Methods for preparation of keratin fiber color coatings with a carboxylic acid polymer - cdi composition

ABSTRACT

The methods and compositions of the present invention are directed to coloration of anagenic hair. The methods involve priming and deep cleaning the anagenic hair followed by coating the hair strands with a composite pigment containing film of a small molecule and a film forming composition which covalently interact to form an intimate three dimensional silicone network incorporating the pigment on the surfaces of the hair.

BACKGROUND

The recent two decades have seen significant effort directed toward development of external hair coloring technology that can be characterized as permanent but avoids bleach and penetration of dye precursors into the keratin fiber cortex. This technology in the main involves production of coloration of hair strands without involving the cortex. Hair coloration can be achieved by coating the surfaces of keratin fibers with a cosmetically acceptable polymer film containing pigment particles or with multi-layer polar attractive films containing coloration dyes instead of pigments. Numerous difficulties have plagued non-cortex hair coloration, however. Water soluble polymer films are easily removed by shampoo. Water insoluble and multi-layer films seem to have better remanence but they also typically survive only two or three shampoo washings. Film inflexibility, film irregularity, film thickness, inability to distribute color appropriately throughout hair tresses, film weakness and film dissolution through solvation, polar and/or ionic interaction with shampoo, organic liquids and other hair dressing components deliver undesirable tactile responses and physical displacement of the polymer film. These difficulties lead to flaking, hair strand breakage, artificial appearance, and irregular, undesirable color removal.

Hair coloring technology has made progress over the past five years in solving these issues. Better remanence and development of elasticity of the color coating on the hair tresses have been achieved by various technologies. Additional improvements include development of techniques for combinations of various pigments and pigment distribution designed to mimic at least to some extent natural highlights of hair.

The kinds of coatings span a range of organic, silicone, organosilicone compositions to biological protein derivative compositions. Mixtures and layers of coatings are typical in this respect. Suitability and compatibility of such mixtures and layers and their interactions with hair and scalp are problematic. Failure to establish compatible inter-surface connections can lead to coatings exhibiting flaking, roughness, stiffness, irregular films, lack of flexibility, rough texture, touch and feel, and lack of remanence. Strong inner-coating and keratin fiber connections can lead to coatings that exhibit stiffness, flaking, thick texture/feel and extreme difficulty in attempts to remove and/or replace the coating with another coating. Rapid setting and lack of flowability of the compositions for application can lead to patchy coverage instead of contiguous coating formation.

When such coatings have been combined with keratin fibers such as hair, esthetically pleasing coloration with long remanence has proved impossible to achieve at present due to the intrinsic qualities of anagenic hair. To date, experimentation to develop keratin fiber coloration such as hair coloration has focused on the use of hair tresses or swatches. These tresses are formed of natural hair but are detached from source (a person) and are usually preprocessed to deliver ease of use for experimental purposes. Such tresses do not enable experimentation and exploitation of the issues and problems intrinsic with anagenic hair, i.e., hair growing from the scalp of a person. Anagenic hair differs from hair tresses because of hair root, mid-length and tip color differences of anagenic hair, keratin structural differences among and between root, mid and end portions of a living hair, continuous sebum secretions extending from the root to the end portion of each strand of anagenic hair, the individual differences in sebum compositional components from person to person, anagenic hair strand dimension, individualized topographic character of strand surfaces and compositional differences from person to person, the fatty acid or F layer, the variation of curl and color of differing regions of anagenic hair on the scalp, scalp skin issues and environmental factors. Additional differences of anagenic hair relative to hair tresses include but are not limited to lack of cleanliness of anagenic hair, presence of pre-existing hair treatments including but not limited to hair styling formulations, permanent oxidative dye applications, permanent wave and/or curl treatment, application of oils and smoothing compositions and conditioning treatments typically applied to anagenic hair. Still other difficulties involve regulatory requirements and the need to avoid tissue damaging and/or environmental attack by sunlight, UV, wind, rain and airborne chemicals, degrading chemicals in water and in hair care and hair dye compositions, as well as sweat and sebum.

Achievement of a truly successful hair coloration technology focuses on experimentation designed to address these problems and issues intrinsic with anagenic hair. While coatings with pigments provide a good starting point, connection of this technology to anagenic hair has yet to be achieved because of these intrinsic problems and issues. Hair coloration technology has demonstrated remanence and a modicum of natural color mimic when applied to tresses. Nevertheless, this technology has failed to demonstrate success when transferred from tresses to anagenic hair.

SUMMARY OF THE INVENTION

These and other difficulties are addressed by aspects of the present invention. The present invention meets these objectives through the design and application methods to enable development of coloration of keratinous fibers such as, but not limited to, hair tresses, hair tresses designed to mimic anagenic hair, anagenic hair, eyebrow hair and eyelash hair, more preferably anagenic hair. The design and application of the methods of the invention feature but are not limited to several embodiments including pretreatment methods, film forming composition methods, priming and deep cleaning methods, adjustment of components of each of the methods and control of parameters, conditions and additives for the methods. These multiple design features enable ready methods for application of the compositions to be dressed onto keratin fibers, preferably anagenic hair.

These multiple design features enable achievement of contiguous coating formation under processing parameters that enable unhurried dressing but rapid coating formation when desired. These multiple design features enable robust remanence, long wear-fastness, pleasing texture qualities, uniform color distribution and/or varied color distribution as well as establishing triggers for color coating removal. These multiple design features enable solution of “downstream problems” that can otherwise be associated with anagenic hair. Such downstream problems include but are not limited to development of strong but flexible interconnection between and among coating, pigment and hair strand surfaces, sebum and F layer effects upon such coating interconnections, root idiosyncrasies affecting interaction between color coating and keratin fiber surfaces, the effect of incomplete or ineffective removal of grubbiness, dirtiness, foulness of anagenic hair. In addition, the multiple design features of color coatings benefit the color arrangement, distribution and maintenance of the color of anagenic hair as it is assailed by environmental factors including but not limited to UV rays, shampoo, brushing, combing, rinsing, rain, wind, coverings by scarves and hats, rubbing and drying with towels and hair dryers, hair conditioners, styling hair sprays, hot iron curling and other environmental and hair care factors. At the same time, these multiple design features according to the invention provide tactile, visual, sound and olfactory sensations at least similar to untreated anagenic hair. According to the invention, the design features provide color coatings on keratin fibers, preferably anagenic hair, that deliver texture/tactile properties such as lightness, fluffiness, free flowing, silkiness, non-stickiness and non-matting and other physical interactions to colored keratin fibers, preferably colored anagenic hair, that are similar to the interactions of natural, non-colored keratin fibers, preferably anagenic hair of humans.

These and other aspects of the present invention include but are not limited to embodiments of methods for obtaining color coating of keratin fibers, preferably anagenic hair, embodiments of the color composition and the components thereof, and embodiments associated with methods for treatment of anagenic hair with embodiments of color compositions to form embodiments of color coatings of keratin fibers, preferably anagenic hair. These aspects additionally include qualities of the color coatings that deliver the above-described characteristics for hair coloration on keratin fibers.

An aspect of the invention utilizes inventive embodiments of the color composition and their components to produce embodiments of the color coating on keratin fibers, preferably anagenic hair. The color coating embodiments are produced by curing the color composition embodiments present on the keratin fibers. The color composition is an uncured combination of its components which may be cured to provide the color coating. Embodiments of these components comprise a pretreatment composition and a film forming composition. Embodiments of the pretreatment composition and film forming composition may be applied separately or together to the keratin fibers and converted (e.g., interbonded) according to methods of the invention to produce the color coating of an interconnected, overlapping and/or intermixed film laid onto keratin fibers such as surfaces of anagenic hair strands. The colored coating on the keratin fibers, preferably on anagenic hair, displays desirable characteristics including but not limited to remanence, wash-fastness, resistance to environmental attack. For keratin fibers, preferably anagenic hair, the colored coating delivers elastomeric flexibility to enable free movement of the coated keratin fibers, pleasing texture characteristics similar to uncoated hair, tensile strength to resist flaking and breakage, and color mimicking of appropriate shades for roots, mid-length and tips of keratin fibers.

An aspect of the invention directed to achievement of the color coating on keratin fibers concerns embodiments of the pretreatment composition applied according to method of the invention. Embodiments of the pretreatment composition comprise an organosilicon small molecule with alkoxysilyl groups and/or organoamine groups or optionally an amine polymer.

Another aspect of the invention directed to achievement of the color coating on keratin fibers concerns embodiments of the film forming composition applied according to the methods of the invention. Embodiments of the film forming composition comprise a binder comprising at least one olefinic polymer, silicone polymer or olefinic-silicone block copolymer having at least two pendant and/or terminal carboxylic acid groups and a linker comprising a alkylenyl, aromatic or alkylenyl aromatic polymer having multiple in chain segments of carbodiimide, or a polymer of ester, amide, olefinic, ether, imine, urethane or urea monomeric residues having pendant alkylenyl single carbodiimide groups. The carboxyl groups of the binder and the carbodiimide groups of the linker combine to form a cross-linked polymer net. The linker may also optionally comprise terminal alkoxysilyl groups. These embodiments also comprise one or more microparticle pigments and color bodies. The embodiments of the film forming composition further may comprise at least a substance that functions as an ancillary component for promotion and/or improvement of such characteristics as one or more of coating leveling, promotion of curing, plasticization and flexibility, UV protection, pigment innerconnection with binder and/or linker and similar additive characteristics.

According to embodiments of the methods of the invention, embodiments of the pretreatment composition are applied to keratin fibers before and/or simultaneous with and/or in combination with application of the film forming composition to the keratin fibers. In some instances, the pretreatment composition may be applied and processed at least partially to facilitate condensation-cure of some of the alkoxy silyl groups before application of the film forming composition. In other instances, the film forming composition may be applied immediately after application of the pretreatment composition. In still other instances, the pretreatment composition and film forming composition may be combined together and applied as a mixture to the keratin fibers. Irrespective of the order of addition, the combined pretreatment composition and film forming composition may be cured to effect the carbodiimide-carboxylic acid addition and to effect the alkoxysilyl condensation of the pretreatment composition, optional addition of pretreatment composition amine groups to carbodiimide and the optional condensation of the optional alkoxysilyl groups of the film forming composition with themselves and with the pretreatment composition. Although it is not a limitation of the invention, it is believed that irrespective of the order of addition, the pretreatment composition distributes preferentially to the keratin fiber surfaces so as to enable its interaction with features of the keratin protein at the surfaces of the keratin fibers and with one or more components of the film forming composition.

Further aspects of the embodiments of the invention include at least in part a three-dimensional network of the color coating formed through the acid-carbodiimide (hereinafter acid-CDI) addition, optional amine-CDI addition and alkoxysilane condensation of the color composition components comprising the film forming composition and pretreatment composition. Although it is not a limitation of the invention, it is believed that the initial small molecular size of the components of the pretreatment composition enable intimate networking interaction with keratin fiber surfaces and enable networking interaction with the components of the film forming composition so that the presence of incidental sebum of anagenic hair and subsequent sebum secretion onto anagenic hair do not at least in part remove the color coating from the anagenic hair surfaces.

Yet another aspect of the invention directed to achievement of the color coating on keratin fibers, especially on anagenic hair, concerns embodiments of the priming and/or deep cleaning of the surfaces of the keratin fibers. These embodiments are developed through practice of Praeparatur and Fundamenta techniques. These techniques deal with unique issues of anagenic hair such as but not limited to sebum coating on the keratin fiber strand surfaces, bound fatty acid layer (F layer) attached to keratin fiber strand surfaces, grime, grit, foulness and deposits from hair formulations previously applied to anagenic hair. The Praeparatur technique substantially to essentially primes the hair to remove surface crusting, sebum and/or glazing while the Fundamenta technique deep cleans the surface character and/or surface structure of keratin fibers as well as removes the F layer. These techniques may be applied separately and individually or may be applied together in either sequence. Irrespective of use of both or use of one or the other, these techniques are applied to hair before applying the pretreatment and film forming compositions. It is believed that the combination of one or more of the Praeparatur/Fundamenta techniques coupled with the pretreatment small molecule forming a network intimately adhering to the contours of the treated topographic surfaces of keratin fibers and the adherence among and between the small molecule network and the film forming composition produce a highly remanent color coating on anagenic hair.

Embodiments of the Praeparatur technique include but are not limited to mild agitation with an aqueous surfactant composition to strong interaction with an aqueous or aqueous organic medium with anionic surfactant and/or rinsing with aqueous media optionally having pH adjustment. Additional procedures include optional mechanical agitation with such surfactant media and combing, brushing, vibrating, ultrasound and similar vibratory action applied to the surfaces of keratin fibers.

Embodiments of the Fundamenta method involve restructuring of the hair strand surfaces including F layer removal and include but are not limited to one or more of a non-thermal equilibrium plasma treatment; chemical treatment with a phase transfer tenside such as a multi-alkyl ammonium halide; chemical treatment with an oxidative agent such as persulfate, ozone or a peroxide such as benzoyl peroxide or hydrogen peroxide with optional alkali and optional surfactant cleaning.

Aspects of the invention are directed to embodiments of methods for application of the pretreatment composition, the film forming composition, and Praeparatur and Fundamenta techniques to form a color coating on keratin fibers such as anagenic hair. Embodiments of the methods comprise parameters, conditions and techniques for any one or more of: a) an application of the pretreatment composition to keratin fibers, preferably anagenic hair; b) an application of the film forming composition to keratin fibers, preferably anagenic hair; c) Praeparatur techniques applied to keratin fibers, preferably anagenic hair; and d) Fundamenta techniques applied to keratin fibers, preferably anagenic hair or any combination of these methods to form a color coating on keratin fibers, preferably anagenic hair.

The methods of the invention involving parameters, conditions and techniques for application of film forming composition may be directed to application of the film forming composition alone to keratin fibers. However, it is preferred that the methods of the invention involve parameters, conditions and techniques for application of the pretreatment composition to keratin fibers, preferably anagenic hair before, or simultaneous with, or mixed with, or in combination with the application of film forming composition. Additionally, application of sequential and/or simultaneous and/or mixed combinations of the pretreatment composition and the film forming composition may call for prior application of Praeparatur and/or Fundamenta techniques to keratin fibers, preferably anagenic hair.

According to the invention, the desirable characteristics of the color coatings on keratin fibers, preferably anagenic hair, may be demonstrated by tests of the coloration on hair tresses prepared from unbleached natural white human hair (hereinafter untreated hair tresses), bleached natural white human hair (hereinafter treated hair tresses) and untreated hair tresses specially prepared with sebum so as to mimic anagenic hair (hereinafter mimic hair tresses). The two base line forms of hair tresses (untreated and treated hair tresses) are not anagenic hair in that they are cut natural hair so that they are not bathed in sebum secretion but nevertheless have the F layer coating. The untreated hair tresses are substantially hydrophobic, have low porosity and have little or no keratin protein surface disruption. The treated hair tresses are substantially less hydrophobic to more hydrophilic than, and have greater porosity than, the untreated hair tresses. The treated hair tresses also display low to mild keratin protein surface disruption. The mimic hair tresses are especially treated to demonstrate the sebum, F layer, grubbiness, foulness, and root, mid-length and tip issues associated with anagenic hair and especially those associated with the root segment of anagenic hair, The root segment of anagenic hair is constantly bathed in sebum and has the F layer coating so that the root segment of anagenic hair shows the most extreme behavior difference relative to treated and untreated hair tresses. To establish the mimicry, the untreated hair tresses undergo a series of preparations designed to establish a close comparison with the behavior of anagenic hair, especially the root segments. To this end, embodiments of color coatings according to the invention have been studied with anagenic hair, untreated hair tresses, treated hair tresses. The results of these preliminary studies have established the techniques and components for development of these hair tresses to enable their similarity to the behavior of anagenic hair, especially the root segments of anagenic hair. Untreated, treated, and mimic hair tresses are accordingly able to function as the substrates for experimental development of the embodiments of the color coatings and methods for hair coloration with anagenic hair.

When color coatings are formed onto untreated and onto treated tresses, long lasting remanence is exhibited. However, when the same color coatings are applied to anagenic hair such as the hair of a live salon hair model, remanence disappears. For efficiency of experimental practice, the above described mimic hair tress has been developed to come as close as possible to the behavior of anagenic hair, especially the root segments of anagenic hair. Through use of the mimic hair tress, it has been surprisingly discovered that the combination of the Praeparatur and Fundamenta techniques and the small molecule pretreatment network coupled with the acid-CDI binder-linker preserve remanence for color coatings on mimic hair whereas those color coatings on mimic hair prepared without application of the Praeparatur and/or Fundamenta techniques demonstrate significant to almost full fading during the multiple shampoo applications designed to examine remanence in real life conditions.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 illustrates a color gamut plot.

FIG. 2 illustrates a color combination plot.

FIG. 3 illustrates a color combination plot.

FIG. 4 illustrates a color combination plot.

FIG. 5 illustrates a color combination plot.

FIG. 6 illustrates a color combination plot.

DEFINITIONS

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art.

As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise.

The term “may” in the context of this application means “is permitted to” or “is able to” and is a synonym for the term “can.” The term “may” as used herein does not mean possibility or chance.

The term and/or in the context of this application means one or the other or both. For example, an aqueous solution of A and/or B means an aqueous solution of A alone, an aqueous solution of B alone and an aqueous solution of a combination of A and B.

The molecular weight of a polymer or oligomer used according to the invention may be measured by a weight average molecular weight, and the distribution of molecules of different molecular weights of a polymer or oligomer used according to the invention is determined by its polydispersity. Molecular weight is expressed as daltons (Da), kiloDaltons (KDa) and megaDaltons, which is million daltons or (MDa). The acronym Mw stands for weight average molecular weight, M_(n) is the number average molecular weight of a given polymer. Polydispersity is a unit-less number and indicates the breadth of the distribution of the polymer molecular weights and is defined as the M_(w)/M_(n).

The term “about” is understood to mean ±10 percent of the recited number, numbers or range of numbers.

The term “about 0 wt %” is understood to mean that no substance, compound or material to which zero (0) refers is present, up to a negligible but detectable amount is present, assuming that the detectability can be determined on a parts per million basis.

Where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognize that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group. For example, if X is described as selected from the group consisting of methyl, ethyl or propyl, claims for X being methyl and claims for X being ethyl and X being propyl are fully described. Moreover, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognize that the invention is also thereby described in terms of any combination of individual members or subgroups of members of Markush groups. Thus, for example, if X is described as selected from the group consisting of bromine, chlorine, and iodine, and Y is described as selected from the group consisting of methyl, ethyl, and propyl, claims for X being bromine and Y being methyl are fully described.

If a value of a variable that is necessarily an integer, e.g., the number of carbon atoms in an alkyl group or the number of substituents on a ring, is described as a range, e.g., 0-4, what is meant is that the value can be any integer between 0 and 4 inclusive, i.e., 0, 1, 2, 3, or 4. Similarly, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range were explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.

Keratin fibers means any natural keratin material containing keratin protein including hair, eye brows and eyelashes. Natural keratin fibers include those from mammals and/or on mammals including human, primate, ruminant, camelid, equine, rodent and neovison including but not limited to cow, sheep, deer, goat, buffalo, lama, alpaca, camel, guanaco, vicuna, horse, antelope, moose, elk, rat, mouse, beaver, rabbit, mink, monkey, ape and similar species. Natural keratin material may include hair and fur. Keratin fibers include scalp hair, eyebrow hair and eyelash hair. Keratin fibers may be removed from their source such as hair cut from the scalp of a living person or may mimic anagenic hair when treated with sebum. As used herein keratin fibers includes cut hair, mimic hair tresses and anagenic hair. For experimental purposes, keratin fibers are formed into tresses. A tress is a shock of keratin fibers e.g., hair, held in a clamp at one end and free at the other end. The hair on the head of the average person weighs about 100 g. A tress is formed with about 1 gram of hair or about 1/100 the weight of the hair on the head of a person. Typical commercial hair products for application to hair weigh about 100 to 120 g which translates into about 1 g of product per gram of a person's hair. This relationship establishes the amount of experimental product to be applied to a tress of hair, 1 gm of experimental product per tress weighing about 1 g.

As used herein “anagenic hair” means hair strands that are in direct connection with a hair follicle which is in either the anagen or telogen state. Anagenic hair is present in one of these states on a scalp of a person, a human. The follicle of anagenic hair produces long chain fatty acids, so-called F-layer, which form a water resistant coating on the cuticle of the hair shaft. Joining the hair follicle channel is a sebaceous gland that secretes sebum onto the hair shaft and onto the scalp. As a strand of hair grows from the follicle and extends from the scalp, sebum produced at the follicle spreads out from the follicle and continues to coat the strand. Sebum is removed at least in part from strand ends by shampooing but is replenished by this continued production. Hair cut from a living person is no longer anagenic hair.

As used herein, the terms “covalent, coordinate, electrostatic, ionic, dipolar and entanglement or entwining interactions” mean a chemical relationship between two atoms or two groups of atoms. The interaction includes a covalent bond between the atoms such as the covalent bond between the two carbons of ethane. The interaction includes a coordinate bond between two or more atoms such as the coordinate bond between oxygen and sulfur of the sulfate anion (SO₄ ⁻²) or a complex of zinc and EDTA. The interaction includes an electrostatic or ionic interaction between two charged atoms or particles such as the interaction between sodium and chloride of salt or between ammonium and acetate of ammonium acetate. Dipolar interaction includes hydrogen bonding such as the interaction between water and the hydroxyl of methyl alcohol. The interaction includes entanglement or entwining which is lipophilic interaction or mechanical/physical twisting together such as is present in the molecules of polyethylene.

Adherence as used herein generally refers to an arrangement in which a substance formed of a polymer, oligomer or small molecule exhibits a connective aspect with another material such as another polymer, oligomer, small molecule, keratin protein, through such forces as covalent bonding, hydrogen bonding, coordinate interaction, electrostatic interaction, dipolar interaction, small force interaction, dispersion force at least as a result of entropy, molecular entanglement, mechanical interaction as may be exhibited on a molecular level by a molecular chain wrapping around irregular terrain features of a surface. Adherence in this context may be, but not necessarily, shown by the inability of the adhered material to be removed from the substance without exertion of any force.

Entanglement as used herein generally refers to an arrangement in which a chain crosses an arbitrary plane 3 times. The chain is then entangled. If the chain is shorter and crossed only two times, it can be pulled in the middle and both ends will release without being bound. With three crossings, if the chain is at one point, it will trap another polymer chain at a different place.

As used herein, the term “transfer resistance” or rub off resistance generally refers to the quality exhibited by colored coatings that are not readily removed by contact with another material, such as, for example, an item of clothing or the skin. Transfer resistance can be evaluated by any method known in the art for evaluating such transfer. For example, transfer resistance of a colored coating can be evaluated by the amount transferred from a wearer to any other substrate after the expiration of a certain amount of time following application of the colored coating to the hair. The amount of colored coating transferred to the substrate can then be evaluated and compared. For example, a colored coating can be transfer resistant if a majority is left on the wearer's hair. Preferably little or no colored coating is transferred to the substrate from the hair.

As used herein, the term “minimally alters the keratin fibers, upon application” generally means that after removal of the composition coating on the keratin fibers, the keratin fibers are returned to a substantially unaltered state. The state of the keratin fibers can be assessed for example using ATR FT-IR for oxidative damage as described later or through tensile testing methods known to those skilled in the art for assessing fiber strength for example using equipment such as those designed and sold by Dia-Stron™.

As used herein, the term “converting” means causing covalently co-reactive pairs of components of a composition such as but not limited to the binder and linker of the film forming composition to react together chemically to produce the reacted form such as, for example a chain-extended and/or cross linked polymer functioning as coating or film. Converting is accomplished by the application of an activity designed to cause the covalent bonding of the reactive groups or pairs of the co-reactive components. Activities enabling conversion include but are not limited to drying, heating, curing as in causing the curing/reacting together the co-reactive components, allowing the co-reactive components to combine or mix at standard conditions without further intervention, addition of a catalyst, changing pH of the composition and any other activity that is capable of influencing the reactivity and/or rate of the reaction of the co-reactive components.

“Aliphatic substituent, group or component” refers to any organic group that is non-aromatic. Included are acyclic and cyclic organic compounds composed of carbon, hydrogen and optionally of oxygen, nitrogen, sulfur and other heteroatoms. This term encompasses all of the following organic groups except the following defined aromatic and heteroaromatic groups. Examples of such groups include but are not limited to alkyl, alkenyl, alkynyl, corresponding groups with heteroatoms, cyclic analogs, heterocyclic analogs, branched, dendritic, star or fullerene-like and linear versions and such groups optionally substituted with functional groups, as these groups and others meeting this definition of “aliphatic” are defined below.

“Aromatic substituent, group or component” refers to any and all aromatic groups including but not limited to aryl, aralkyl, heteroalkylaryl, heteroalkylheteroaryl and heteroaryl groups. The term “aromatic” is general in that it encompasses all compounds containing aryl groups optionally substituted with functional groups (all carbon aromatic groups) and all compounds containing heteroaryl groups optionally substituted with functional groups (carbon-heteroatom aromatic groups), as these groups and others meeting this definition of “aromatic” are defined below.

As used herein, the term “optionally” means that the corresponding substituent or thing may or may not be present. It includes both possibilities.

“Alkyl” refers to a straight or branched, dendritic, star or fullerene-like or cyclic hydrocarbon chain group consisting solely of carbon and hydrogen atoms, unless otherwise specifically described as having additional heteroatoms or heterogroups. The alkyl group contains no unsaturation, having from one to twenty four carbon atoms (e.g., C₁-C₂₄ alkyl). Whenever it appears herein, a numerical range such as for example but not limited to “1 to 24” refers to each integer in the given range; e.g., “1 to 24 carbon atoms” means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 24 carbon atoms, although the present definition also covers the occurrence of the term “alkyl” where no numerical range is designated. In some embodiments, it is a C₁-C₄ alkyl group. In other instances, it is a C₁-C₆ alkyl group and in still other instances it is a C₁-C₂₄ alkyl group. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, hexyl, septyl, octyl, nonyl, decyl, and the like. The alkyl is attached to the rest of the molecule by a single bond, for example, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (iso-propyl), n-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), 3-methylhexyl, 2-methylhexyl, and the like.

“Alkylenyl” refers to a straight or branched, dendritic or star divalent hydrocarbon chain consisting solely of carbon and hydrogen atoms, unless otherwise specifically described as having additional heteroatoms or heterogroups. The alkylenyl group contains no unsaturation, has a dangling valence bond at either end of the chain for bonding to two other moieties. The alkylenyl group may have a carbon number range of 1 to 24 carbon atoms unless otherwise specified. In all cases the general and specific numerical range of carbon atoms includes each integer in the range. An example of a divalent hydrocarbon chain designated as an alkylenyl group is as follows: —CH₂—CH₂—CH₂—CH₂—; the dashes (-) indicate valence bonds to other atoms or moieties not shown. This example of an alkylenyl group is butylenyl.

“Cycloalkyl” is a subcategory of “alkyl” and refers to a monocyclic or polycyclic group that contains only carbon and hydrogen, and may be saturated, or partially unsaturated. Cycloalkyl includes one or more rings, such as two or three or four rings either linked in tandem or through alkyl group or fused.cycloalkyl groups include groups having from 3 to 24 ring atoms (i.e., C₃-C₂₄ cycloalkyl). Whenever it appears herein, a numerical range such as but not limited to “3 to 24” refers to each integer in the given range; e.g., “3 to 24 carbon atoms” means that the cycloalkyl group may consist of 3 carbon atoms, etc., up to and including 24 carbon atoms. In some embodiments, it is a C₃-C₈ cycloalkyl group. In some embodiments, it is a C₃-C₅ cycloalkyl group. Pursuant to the definition of alkylenyl, a cycloalkyenyl group is a monocyclic or polycyclic group with two dangling valences for bonding to two other moieties. Illustrative examples of cycloalkyl groups include but are not limited to the following moieties: cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloseptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, and the like.

“Alkoxy” refers to the group —O-alkyl, including from 1 to 24 carbon atoms of a straight, branched, dendritic, star or cyclic configuration and combinations thereof attached to the parent structure through an oxygen. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, cyclohexyloxy and the like. “Lower alkoxy” refers to alkoxy groups containing one to six carbons. In some embodiments, alkyl is an alkyl group which encompasses both linear, branched, dendritic, star or fullerene-like chain alkyls of multiple carbon atoms. Without further definition of the number or carbon atoms present, as used herein, the term “alkoxy” such as an alkoxysilyl group means a C₁-C₆, preferably C₁-C₄, more preferably C₁-C₂ alkoxy such as methoxy and ethoxy.

The term “alkoxysilyl” refers to a siloxane moiety substituted by three alkoxy groups, in other words a trialkoxysilyl group, and in which the silicon atom joins either a carbon or an oxygen depending upon the identity of the moiety to which the alkoxysilyl group is bound, such as but not limited to an organic compound, a siloxane compound, an organosiloxane compound, an organic polymer backbone, a silicone polymer backbone or an organosilicone backbone. Thus, the term “alkoxysilyl” as used herein is a synonym and means a trialkoxysilyl group, in other words —Si(OR)₃ in which R is an alkyl group of 1 to 6 carbons, preferably 1 to 3 carbons and more preferably methyl or ethyl. Also, because the hydrolysis intermediate of each alkoxy of the alkoxysilyl group is hydroxy group as in hydroxysilyl, the hydroxysilyl group is included in this definition. One of the alkoxys of the alkoxysilyl group may hydrolyze and the resulting hydroxysilyl may condense with another hydroxysilyl group derived from the corresponding alkoxysilyl group to form an Si—O—Si bond. Because there are three alkoxy groups on this moiety, the formation of a silicon-oxygen-silicon bond may occur as many as three times for a single alkoxysilyl (trialkoxysilyl) group. Irrespective of whether the alkoxysilyl group is pendant or terminal on a molecule such as a small molecule, oligomer or polymer, this multiple Si—O—Si bonding arrangement for a single alkoxysilyl group means that the molecule with the single alkoxysilyl group may undergo multiple condensations. The molecule with an alkoxysilyl may be chain extended with another molecule with an alkoxysilyl to produce a linear chain extended molecule. This linear chain extended molecule contains additional Si—OR functions at this Si—O—Si chain extension. These additional Si—OR functions can again condense with a corresponding Si—OR function of another linear chain extended molecule. The result is a cross-link at the intermediate section of these molecules bearing the Si—O—Si link. These additional Si-OR's of separate chain extended molecules can therefor condense to cross link the separate chain extended molecules.

“Amino” or “amine” refers to an —N(R^(a))₂ group, where each R^(a) is independently hydrogen or an alkyl group of 1 to 3 carbons, e.g., methyl, ethyl or propyl.

“Aryl” is a subcategory of aromatic and refers to a conjugated pi ring or multiple rings with six to twenty two ring atoms. The aryl group has at least one ring having a conjugated pi electron system which is carbocyclic (e.g., phenyl, fluorenyl, naphthyl and anthracenyl). Included are partially saturated aryl rings such as tetrahydro naphthyl.

“Heteroalkyl” “heteroalkenyl” and “heteroalkynyl” include optionally substituted alkyl, alkenyl and alkynyl groups and which have one or more skeletal chain atoms selected from an atom other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus or combinations thereof. A numerical range may be given, e.g. C₁-C₂₄ heteroalkyl which refers to the chain length in total, which in this example may be as long as 24 atoms long. For example, a —CH₂OCH₂CH₃ group is referred to as a “C₄” heteroalkyl, which includes the heteroatom center in the atom chain length description. Connection to the rest of the molecule may be through either a heteroatom or a carbon in the heteroalkyl chain.

“Heteroaryl” or heteroaromatic refers to a 5, 6 or 10-membered aromatic group (e.g., C₅-C₁₃ heteroaryl) that includes one or more ring heteroatoms selected from nitrogen, oxygen and sulfur, and which may be a monocyclic, bicyclic, tricyclic or tetracyclic ring system or a conjugated ring system such as cyclopentadienyl optionally with a bridging atom providing conjugation such as pyrrole or ferrocenyl. Whenever it appears herein, a numerical range refers to each integer in the given range. An N-containing “heteroaromatic” or “heteroaryl” moiety refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom. The polycyclic heteroaryl group may be monocyclic or non-monocyclic. The heteroatom(s) in the heteroaryl group is optionally oxidized. One or more nitrogen atoms, if present, are optionally quaternized. The heteroaryl is attached to the rest of the molecule through any atom of the ring(s). Examples of heteroaryls include, but are not limited to pyrrolyl, furanyl, thiophenyl, imidazolyl, pyranyl, pyridinyl, pyrimidinyl, benzimidazole, benzothiophenyl, quinolinyl, quinazolinyl, and similar heteroaryl compounds of 6 to 12 carbons and 1, 2 or 3 heteroatoms including any combination of nitrogen, oxygen and sulfur.

“Heterocyclic” refers to any monocyclic or polycyclic moiety comprising at least one heteroatom selected from nitrogen, oxygen and sulfur. As used herein, heterocyclyl moieties can be a partially saturated aromatic ring or a saturated monocyclic or polycyclic ring wherein the ring may be formed of 3 to 8 atoms.

The term “polymer” or “Poly” means any one or more of an organic, silicone or organosilicone compound formed from multiple monomeric units. The units may be identical or may be a combination of units of differing identities. The number of units present may range from at least 2 to compounds having very large number of units. Typical weight average molecular weights of a polymer may range from less than one hundred Da to a million or more Da.

Compounds and groups including a polymer (e.g., Poly), an alkyl, an alkylenyl, a carbon or silicone chain, a carbon or silicon backbone, an aliphatic group of multiple carbons, hetero forms of any of the foregoing compounds and groups, as well as groups including aromatic, heteroaromatic cycloalkyl heterocycloalkyl or hetero forms thereof bearing any of these foregoing compounds and groups may have a structural configuration of linear, branched, star or dendritic which is a subcategory of branched. A preferred configuration is branched or linear and a more preferred configuration is linear. Use of any of these compound or group names without indicating a particular configuration incorporates all of these configurations and means that linear and/or branched is preferred and linear is most preferred.

The terms “In situ linking” and “in situ linkable” and “Cross linkable” mean the potential at a future time to form covalent bonds to provide interactions and/or connections between molecules. The terms “in situ linked” and “cross linked” mean that in the present state, covalent bonds have already occurred.

“in situ” is a Latin phase meaning in its original place. In the context of this invention, it means an activity such a cross linking that takes place on the hair.

The average reactive functional group equivalent weight as used herein means for a reactive functional group of a complementary pair, the ratio of the weight average molecular weight of the polymer, oligomer or small molecule containing the reactive functional group to the average number of occurrences of that reactive functional group in the polymer, oligomer or small molecule. If the Mw of a polymer is 1 KDa and the average number of occurrences of the reactive functional group in the polymer is 2, the Mw for the reactive functional group equivalent weight is (1 KDa)/2 or 500 Da.

Coefficient of thermal expansion refers to the fractional increase in length of a species per Celsius increase in temperature at a constant pressure with a starting temperature of 25° C.

Zeta potential relating to pigment microparticles means the electrokinetic potential of extremely small particles suspended in colloidal dispersions. It is caused by the net electrical charge at the particle interface with the suspending fluid. It is an indicator of the stability of a colloidal dispersion. The magnitude indicates the degree of electrostatic repulsion between adjacent similar charged particles in a dispersion. At zero or minimal + or − potential, rapid coagulation can occur. At a + or − zeta potential above about 40 mV, good colloidal stability is maintained. Zeta potential can be measured using approaches known to those skilled in the art. For example, a Zetasizer Nano Z from Malvern Panalytical Ltd, Malvern U.K. may be used to assess the zeta potential of the components.

Microfibril length as used herein general refers to a distribution of lengths for any given microfibril, and the fiber length refers to the average fiber length, assessed over a minimum of 10 fibers chosen randomly from a sample of the microfibrils. The length refers to the end to end distance along the major axis of the material and is not a measure of the cross sectional width.

Hansen Solubility Parameters constitute a technique for characterizing solubility, dispersion, diffusion, chromatography and related topics for a particular material. The material such as a solvent or solute can be characterized by three parameters δD for Dispersion (van der Waals), δP for Polarity (related to dipole moment) and δH for hydrogen bonding. See “Hansen Solubility Parameters— A User's Handbook”, CRC Press, Boca Raton, 2007, ISBN-10: 0849372488.

Hydrogen bonding refers to a weak bond between two molecules resulting from an electrostatic attraction between a proton in one molecule and an electronegative atom in the other. Ionic bonding refers to a type of chemical bonding that involves the electrostatic attraction between oppositely charged ions.

Young's modulus, or the Young modulus, is a mechanical property that measures the stiffness (e.g., stretchiness) of a solid material. It defines the relationship between stress (force per unit area) and strain (proportional deformation) in a material in the linear Hookean elastic regime of a uniaxial deformation. In other words, the ability of a material to withstand changes in length when under lengthwise tension or compression.

The term Tg or glass transition temperature refers to the temperature range through which a material, such as but not limited to a polymer, transitions from amorphous solid-like or glass-like properties at a lower temperature to viscous or rubber-like properties at a higher temperature. The transition is not a phase transition such as solid to liquid. Embodiments of the color coatings on mimic hair, treated hair and untreated hair typically will exhibit a Tg range well below ambient temperature so that the films produced will exhibit flexible, elastomeric, smooth physical properties.

The term ultimate compression refers to the amount of compression a given material can experience under a specific test method before failure occurs and the material breaks.

A nanoemulsion is a liquid/liquid, liquid/solid, liquid/gas or gas/gas composition in which there is at least one discontinuous phase dispersed in a continuous phase and in which the average particle or micellar diameter of the discontinuous phase is in the range 10 nm-300 nm.

The term “sebum” is an oily, waxy substance produced by the sebaceous glands of the human body. It coats, moisturizes, and protects skin and hair. Sebum is primarily composed of triglycerides (≈41%), wax esters (≈26%), squalene (≈12%), and free fatty acids (≈16%). The sebum used to form mimic hair is a Hautfett nach BEY, sold by Wfk-Testgewebe GmbH which comprises 18.0% free fatty acids, 32.8% beef tallow, 3.6% triglycerides, 18.3% wool fat, 3.7% cholesterol, 12.0% hydrocarbons, 11.6% cutina.

The term “surface energy” quantifies the disruption of intermolecular bonds that occurs when a surface is created. The surface energy may be defined as the excess energy at the surface of a material compared to the bulk, or it is the work required to build an area of a particular surface. Perhaps the most widely used definition of surface energy, historically, is that of Zisman (“Relation of Equilibrium Contact Angle to Liquid and Solid Constitution”, W. A. Zisman, ACS Advances in Chemistry Series #43, 1961, pp. 1-51). Zisman defines the surface energy of a solid to be equal to the surface tension of the highest surface tension liquid (real or imaginary) that will completely wet the solid, with a contact angle of 0°. This comes from the widely observed tendency of contact angle to decrease as liquid surface tension decreases on the same solid sample. A Zisman plot is created for a test surface using a series of different probe liquids with known surface tensions, with the known surface tensions plotted on the x axis, and the cosine of the resulting contact angle with the test surface plotted on the y axis. The highest surface tension when the cosine of the contact angle reaches 1 is determined to be the surface energy of the test substrate. The Owens/Wendt theory (Owens, D. K.; Wendt, R. C.; Jour. of Applied Polymer Science, 13, 1741, (1969)) is a further development to measure the surface energy of a test substrate. It considers the surface energy being comprised of two components—a dispersive component and a polar component. The dispersive component accounts for van der Waals and other non-site specific interactions that a surface is capable of having with applied liquids. The polar component theoretically accounts for dipole-dipole, dipole-induced dipole, hydrogen bonding, and other interactions which a surface is capable of having with applied liquids. Owens and Wendt developed a two parameter model for describing surface interactions, as opposed to the one parameter model of Zisman. The units of surface energy are mN m⁻¹.

The terms “priming” and “deep cleaning” refers to the substantial to essentially complete removal of sebum and F-layer substances from the surfaces of anagenic hair and also refers to removal of synthetic sebum and F layer substances on mimic hair tresses. The Praeparatur and Fundamenta techniques accomplish the priming and deep cleaning of keratin fiber surfaces. Practice of these techniques may accomplish disruption of the keratin fiber surfaces so as to expose variable surface topography and gain an intimate interaction with agents small enough to access the variations of the topography.

DETAILED DESCRIPTION

The present invention is directed to methods and compositions for development of color coatings on keratin fibers, particularly anagenic hair. These methods and compositions may also be applied to keratin fibers relating to all sources such as hair tresses, animal hair and similar keratin fibers. The qualities and properties of the aspects of the pretreatment composition, the film forming composition, their combination as the color composition, the conversion thereof to a film, the Praeparatur and Fundamenta techniques and methods of application contribute to, enhance and promote qualities of the resulting color coating so that the coated keratin fibers and especially coated mimic tresses and anagenic hair demonstrate significant remanence while also demonstrating a performance similar to that of young, uncoated, vibrant, attractive hair of the scalp. To accomplish this aspect, the color coating exhibits qualities including but not limited to flex, stretch and bend, integrity of continuous film under flex, stretch and bend conditions, wash-fastness, remanence, color coordination and resistance to degradation and damage caused at least by, but not limited to, UV radiation, sebum, F layer, sweat, rain, wind and/or environmental attack.

The Method for Forming a Color Coating on Keratin Fibers

Embodiments of the method for forming the color coating on keratin fibers involve the steps of application of compositional embodiments to the surfaces of the keratin fibers to form a composite film on the surface followed by converting the composite film to the color coating on the surfaces of keratin fibers. The compositional embodiments include a pretreatment composition and a film forming composition. The pretreatment composition comprises a medium and an organosilicone small molecule with at least alkoxysilyl groups and/or organoamine groups or optionally with certain aminopolymers such as PEI. The film forming composition comprises a medium, a binder with carboxylic acid groups and a linker with carbodiimide groups. The film forming composition also comprises pigment microparticles and color bodies. The binder, linker and pigment/color body components of the film forming composition are maintained separately in media and are mixed prior to use. The pigment/color body component comprises groups of preformulated differently colored microparticle pigments/color bodies optionally coated with the organosilicone small molecule of the pretreatment composition dispersed in a dispersant medium. Selections from the groups of differently colored pigments may be pre-blended and provided as a wide number of choices of pre-formulated shades and hues for the hair to be colored. Alternatively, basic pigment formulas may be provided, custom blended and combined with the film forming composition just before use so as to provide the desired color shade and hue for the hair to be colored.

To prepare the keratin fibers, especially anagenic hair, for coloration, the keratin fibers are primed and deep cleaned with either, or both in any order, of the Praeparatur and Fundamenta techniques. As explained above, priming and deep cleaning combined with the pretreatment and film forming compositions delivers a color coating on anagenic hair that displays significant remanence.

The Film Forming Composition

Embodiments of the film forming composition are directed to multiple components comprising a binder and a linker that are adapted to combine in situ to crosslink through a carboxylic acid-carbodiimide (acid-CDI) addition. The binder comprises an olefinic polymer, silicone polymer or olefinic-silicone block copolymer having at least 2 pendant and/or terminal carboxylic acid groups. The binder is preferably linear or branched, more preferably linear. The linker comprises a alkylenyl, aromatic or alkylenyl aromatic polymer having multiple in chain segments of carbodiimide; or a polymer of ester, urethane or urea monomeric residues having pendant alkylenyl single carbodiimide groups. The linker is preferably linear or branched, more preferably linear. The film forming composition further comprises one or more microparticle pigments and/or color bodies. The film forming composition also comprises a medium in which the multiple components, pigment(s) and/or color bodies are dispersed, mixed and/or otherwise contained. The film forming composition may but not necessarily further comprise one or more ancillary components as adjuncts for helping and/or promoting characteristics of the color coating on keratin fibers. Application of the film forming composition to keratin fibers may also include a conversion step such as drying and curing to evaporate residual medium from the film forming composition on the surfaces of the keratin fibers and to cause the acid-CDI addition reaction thereby producing a chain extended, crosslinked polymer network comprising a film.

The binder and linker components of the film forming composition are separately maintained until immediately prior to use. The film forming composition is prepared for use for application to keratin fibers by combining and mixing the binder and linker components in media according to the proportional quantities described below. The pigment/color bodies with dispersant may also be combined as described below to form the film forming composition with pigment/color bodies.

Binder

The binder may be a homopolymer, a copolymer, a terpolymer or a multiple block polymer having at least two carboxylic acid groups. Moreover, the polymeric nature of the binder may be as an organic polymer, a silicone polymer or organosilicone polymer, each of which is configured to have a linear and/or branched configuration, preferably a linear configuration.

In particular, embodiments of the binder of the film forming composition comprise an olefinic, silicone or organosilicone polymer of Formula I having at least two carboxylic acid groups.

MUE-(MU1)_(x)(MUX)_(y)-(MU2)_(z)-(MU3)_(a)(MU3X)_(b)-MUE   Formula I

The symbols MUE, MU1, MUX, MU2, MU3 and MU3X stand for monomeric units of the carboxylic acid polymer. The binder of Formula I may be linear or branched, preferably linear. The monomeric units MU1, MUX (X for acid) and MU2 respectively are hydrophobic, acid and hydrophilic olefinic monomeric units. MU3 and MU3X respectively are siloxane units with the X siloxane unit bearing a pendant alkanoic acid group. MUE (E for end) is the termination unit of the polymer and may be any of the olefinic monomeric units or the siloxane unit. An olefinic polymer comprises either or both of MU1 and MU2 combined with MUX and the termini of this polymer (MUE) may be any of these three former monomeric units. If hydrophilic and hydrophobic units are present in the olefinic polymer, these olefinic monomeric units may be randomly distributed throughout the olefin polymer or may form blocks of hydrophilic and hydrophobic units with the carboxylic acid units preferably being within the hydrophilic blocks. A silicone polymer comprises a combination of MU3 and MU3× with its termini being MU3. The carboxylic acid units may be randomly distributed throughout the silicone polymer. An organosilicone polymer comprises blocks of the olefinic polymer and the silicone polymer. The olefinic polymer blocks may have the monomeric units arranged as in the olefinic polymer. The acid containing units may be MUX or MU3X and preferably are MUX. The binder comprising the olefinic, silicone or organosilicone polymer formed of the foregoing monomeric units may linear or branched preferably be linear.

In particular, these monomeric units may be linear or branched, preferably linear and are as follows.

-   -   a) MU1 is a hydrophobic olefinic monomeric unit comprising a         C2-C10 alkene residue, a C4-C12 alkadiene residue and/or a         C6-C10 aromatic/alkylaromatic vinyl residue.     -   b) MU2 is a hydrophilic olefinic monomeric unit comprising a         vinyl C2-C16 alkanoic ester residue, a C1-C14 alkyl or         hydroxyalkyl C2-C14 alkenoic ester residue, a C2-C10 alkenoic         amide residue or N—C1-C4 alkyl substituted version of the amide         residue.     -   c) MUX is an acidic olefinic monomeric unit comprising a C3-C10         alkenoic acid residue or a C4-C10 alkadienoic acid residue.     -   d) MU3 is a dimethylsiloxane monomeric unit.     -   e) MU3X is a monomethylsiloxane monomeric unit bound to an         alkanoic acid of at least 4 carbons with one of the alkyl         carbons of the alkanoic acid optionally having a hydroxy group.     -   f) MUE is a single terminal monomeric unit of MU1, MU2 or MUX         when the polymer is an olefinic polymer or an organosilicone         polymer.     -   g) MUE is a single terminal monomeric unit of MU3 with an         additional methyl, i.e., a trimethylsiloxane unit when the         polymer is a silicone polymer.

The designators x, y, z, a and b indicate the number of the corresponding monomeric units present in the corresponding polymer. Irrespective of the kind of polymer, its molecular size is the sum of x, y, z, a and b which may be an integer of from about 3 up to about 1 million, preferably up to about 300,000, more preferably up to about 250,000, most preferably up to about 200,000. Each of the designators x, y, z, a and b independently indicates the number of corresponding monomeric units forming the linear polymeric backbone. Each of x, z and a may be zero or an integer of from 1 up to about 100,000. Designators y and b indicate the number of acid units present in the polymer with y indicating the number of olefinic carboxylic units and b indicating the number of siloxane carboxylic acid units. Designators y and b may each independently be zero or an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20 provided that at least two carboxylic acid groups are present. Additionally, when the polymer is a silicone polymer b is zero and y is an integer. When the polymer is an olefin polymer, b is an integer and y is zero. When the polymer is an organosilicone polymer one of b and y may be zero and the other an integer or both may be an integer.

Preferred forms of Formula I include:

-   -   a) Formula I in which the designators x and z are each at least         10, designator y is at least 3, designators a and b are both         zero and terminal MUE is MUX. This is the olefinic polymer.     -   b) Formula I in which each of designators x, z and a are 10 to         100, designator y is 1 to 50, designator b is zero, terminal MUE         is MUX. This is the organosilicone block copolymer with olefinic         unit carboxylic acid groups.     -   c) Formula I in which designators x, y and z are zero,         designator a is at least 20, preferably at least 40, designator         b is 1 to 50 and terminal MUE is MU3X or as MU3. This is the         silicone polymer with termini as either dimethylsiloxane bearing         an alkylalkanoic acid group or a trimethylsiloxane unit.     -   d) Formula I in which each of designators x, z and a are 10 to         100, each of designators y and b independently is 1 to 50,         terminal MUE is MUX or MU3. This is the organosilicone polymer         with olefinic and siloxane units bearing the carboxylic acid.

A preferred binder comprises an olefinic or organosilicone polymer with three or more pendant and/or terminal carboxylic acid groups, a weight average molecular weight of from about 0.5 KDa to about 10 KDa, preferably about 0.5 KDa to about 5 KDa; and at least one or more pendant groups selected from an alkyl alkylenylcarboxyate ester group, an alkyl group, an alkylenyloxycarbonylalkyl group and a hydroxalkyl group.

A preferred binder also comprises a silicone polymer with three or more pendant C4-C6 alkanoic acid groups and a weight average molecular weight of from about 0.5 KDa to about 10 KDa, preferably about 0.5 KDa to about 5 KDa.

Another preferred binder of Formula I comprises an olefin polymer of from 3 to 10, preferably 3 to 5 carboxylic acid groups, a weight average molecular weight of from about 0.5 KDa to about 10 KDa, preferably about 0.5 KDa to about 5 KDa; and in which MU1 is butene, pentene, hexene, styrene or any combination thereof; MUX is (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, fumaric acid, maleic acid, itaconic acid glutaconic acid, citraconic acid or mesaconic acid, preferably (meth)acrylic acid, maleic acid, fumaric acid or crotonic acid; MU2 is vinyl acetate, vinyl propanate, vinyl butanate, C1-C3 alkyl or hydroxyalkyl (meth)acrylate, C1-C3 alkyl or hydroxyalkyl crotonate, C1-C3 alkyl or hydroxyalkyl pentanoate, C1-C3 dialkyl or di-(hydroxyalkyl) fumarate, C1-C3 maleate or the corresponding primary amides or C1-C3 alkyl secondary amides or any combination thereof.

Another preferred binder of Formula I comprises a silicone polymer of from 3 to 10, preferably 3 to 5 carboxylic acid groups; the weight average molecular weight of from about 0.5 KDa to about 10 KDa, preferably about 0.5 KDa to about 5 KDa; and in which MU3X is MeSiO—(CH₂)_(n)—CHOH—(CH₂)₂—COOH with n as an integer of from 1 to 6, preferably 2 or 3.

Another preferred binder of Formula I comprises an olefin polymer of from 3 to 10, preferably 3 to 5 carboxylic acid groups, a weight average molecular weight of from about 0.5 KDa to about 10 KDa, preferably about 0.5 KDa to about 5 and in which MU1 is hexene or styrene, MUX is (meth)acrylic acid or crotonic acid, MU2 is vinyl acetate, vinyl C8-C12 isoalkanoate, methyl, ethyl or isopropyl (meth)acrylate or the corresponding hydroxymethyl, hydroxyethyl or hydroxyisopropyl analogs, methyl, ethyl or isopropyl crotonate or the corresponding hydroxymethyl, hydroxyethyl or hydroxyisopropyl analogs.

Another preferred binder of Formula I is an organosilicone block copolymer with carboxylic acid groups in the olefin block. The designators of this preferred binder include designator x as zero meaning no hydrophobic olefinic units, designator b as zero meaning no acid groups pendant to siloxane units, designator a as at least 10 meaning at least 10 dimethylsiloxane units, designator z as at least 10 meaning at least 10 hydrophilic olefinic units, designatory y as 1 to 50 meaning 1 to 50 carboxylic acid olefinic units and MUE is MUX meaning terminal olefinic carboxylic acid units.

Another preferred binder of Formula I is an olefinic polymer comprising at least monomeric units of alkyl (meth)acrylate and/or crotonate, and (meth)acrylic acid and/or crotonic acid. The acid number of this polymer is from about 50 to about 600 preferably about 100 to about 400.

A more preferred binder of Formula I is an olefinic polymer in which the acid monomeric unit is (meth)acrylic acid and/or crotonic acid at about 0.3% to about 75% by weight; the hydrophilic unit is hydroxyethyl or hydroxypropyl (meth)acrylate and/or crotonate at about 0% to about 20% by weight; the hydrophobic monomer is methyl or ethyl (meth)acrylate and/or crotonate at about 5% to about 20% by weight, wherein all weights are relative to the total weight of the polymer.

Exemplary olefinic polymers as the binder include organic copolymers such as acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers such as the product sold under the name Ultrahold 8 and that sold under the name Ultrahold Strong by the company BASF; (meth)acrylic acid/tert-butyl (meth)acrylate and/or isobutyl (meth)acrylate/C1-C4 alkyl (meth)acrylate copolymers such as the acrylic acid/tert-butyl acrylate/ethyl acrylate terpolymer sold by the company BASF under the name Luvimer 100P; (meth)acrylic acid/ethyl acrylate/methyl methacrylate terpolymers and tetrapolymers such as the ethyl acrylate/methyl methacrylate/acrylic acid/methacrylic acid copolymer such as the product sold under the name Amerhold DR-25 by the company Amerchol; methyl methacrylate/butyl or ethyl acrylate/hydroxyethyl or 2-hydroxypropyl acrylate or methacrylate/(meth)acrylic acid tetrapolymers such as the methyl methacrylate/butyl acrylate/hydroxyethyl methacrylate/methacrylic acid tetrapolymers sold by the company Rohm & Haas under the name Acudyne 255.

Additional examples of organic polymers include copolymers of acrylic acid and of C1-C4 alkyl methacrylate and terpolymers of vinylpyrrolidone, of acrylic acid and of C1-C20 alkyl, for example lauryl, methacrylate, such as that sold by the company ISP under the name Acrylidone M and the copolymer of methacrylic acid and of ethyl acrylate sold under the name Luvimer MAEX by the company BASF.

Exemplary silicone polymers bearing pendant carboxylic acid groups as the binder include dual-end carboxy silicones such as X-22-162C from Shin Etsu and Silform INX (INCI name: Bis-Carboxydecyl Dimethicone) from Momentive; single-end carboxy silicone such as X-22-3710 from Shin Etsu. and other carboxy silicones such as Grandsil PCA such as in Grandsil SiW-PCA-10 (INCI name: Dimethicone (and) PCA Dimethicone (and) Butylene Glycol (and) Decyl Glucoside from Grant Industries.

Exemplary organosilicone polymer as binder include multi-block carboxysilicone polymer (tradename Belsil® P1101) having INCI name: Crotonic Acid/Vinyl C8-12 Isoalkyl Esters/VA/Bis-Vinyldimethicone Crosspolymer and a similar organosilicone polymer having the technical name of Crotonic Acid/Vinyl C8-12 Isoalkyl Esters/VA/divinyldimethicone Crosspolymer from Wacker Chemie AG.

Additional exemplary silicone and organosilicone polymer functioning as binder include name HUILE M 642 by the company Wacker, under the names SLM 23 000/1 and SLM 23 000/2 by the company Wacker, under the name 176-12057 by the company General Electric, under the name FZ 3703 by the company OSI and under the name BY 16 880 by the company Toray Silicone as well as Noveon under the name Ultrasil® CA-1 Silicone (Dimethicone PEG-7 Phthalate) and Ultrasil® CA-2 Silicone (Dimethicone PEG-7 Succinate).

Linker

In particular, embodiments of the linker of the film forming composition comprise an organic polymer of Formula II which is a polymer with in-chain carbodiimide groups and may be linear or branched, preferably linear. Alternatively, the linker may comprise an organic polymer of Formula X which is a polymer with pendant single carbodiimide groups and may have a linear or branched backbone, preferably a linear backbone.

Z-(L-N═C═N—)_(p)—Z   Formula II

(Poly)_(q)-(K)_(s)-(Poly)_(r)   Formula X

For Formula II, p is an integer of at least 2. In many instances, L may be the organic group of an organic diisocyanate may be converted to the polycarbodiimide of Formula II. In other instances, L may be an oligomeric or polymeric moiety terminated by isocyanate groups. This formational understanding shows that L may be an organic linker group comprising a saturated aliphatic divalent radical, an aromatic divalent radical or an alkylaromatic divalent radical or a polymer or oligomeric divalent radical with repeating olefinic, carbonate, ester, ether, amide, urethane or urea linkages. Preferably, L is a saturated aliphatic divalent radical, an aromatic divalent radical or an alkylaromatic divalent radical.

For Formula X, each Poly is an organic polymer segment of amide, urea, ester, olefinic, imine monomeric residues. Poly may be based upon a C3 to C6 alkane diamine and a C4-C10 alkane dicarboxylic acid or C4-C10 alkane diisocyanate, or an ester monomeric residue based upon a C3-C6 alkane diol and a C4-C10 alkane dicarboxylic acid and the designators q and r each being an integer of at least 2. Group K provides the pendant carbodiimide group and s is an integer of at least 2. When s is 2 or greater, the resulting multiple K groups are randomly distributed along the Poly backbone including at the termini. Group K comprises Formula XI

For Formula XI, R²⁰ is a C3 to C6 alkylenyl residue and R²¹ is a C3-C6 alkylenyl residue.

For Formulas II and XI, Z may be a non-reactive or reactive terminal group of the polycarbodiimide. As a reactive terminal group, Z may be an —(CH₂)_(n)—Si(OR)₃ in which R is methyl or ethyl and n is an integer of 3 to 6. As a non-reactive terminal group, Z may be a saturated aliphatic monovalent radical, an aromatic monovalent radical or an alkylaromatic monovalent radical.

A preferred linker is Formula II in which L is a saturated aliphatic divalent radical selected from linear or branched or cyclic alkylenyl of 2 to 20 carbons, an aromatic divalent radical selected from benzene or diphenyl, or an alkylaromatic divalent radical selected from p-dimethylenylphenyl or methylenyldiphenyl.

Another preferred linker is Formula II in which L is a saturated alkylenyl divalent radical of 2 to 6 carbons.

Another preferred linker is Formula II in which L is a residue of toluene, diphenylmethane, phenyl, dicyclohexyl methane, methyl-3,5,5,-trimethylcyclohexane, hexane, cyclohexane, norbornane. These L residues are derived from the corresponding diisocyanate compounds.

A more preferred linker is Formula II in which L is dicyclohexylmethane, methyl-3,5,5-trimethylcyclohexane (isophorone) or hexane.

For Formula II and Formula X, a preferred a nonreactive group for Z is a saturated aliphatic monovalent radical selected from linear or branched or cyclic alkyl of 2 to 20 carbons, an aromatic monovalent radical selected from benzene or diphenyl, or an alkylaromatic monovalent radical selected from p-dimethylenylphenyl or methylenyldiphenyl.

A preferred linker as Formula X provides Poly is a polyamide or polyurea and the number of pendant carbodiimide K groups designated by being from 2 to 50, preferably 2 to 10, more preferably 2 to 5.

A method according to any of the preceding statements wherein the linker is Formula X, R²⁰ and R²¹ are each butylenyl or hexylenyl, and Z is butyl or hexyl.

A preferred nonreactive group of Z for Formulas II and X is butane or hexane.

The molecular size of a linker of Formula II and of Formula X is determined by the number of carbodiimide groups and the size of L for Formula II and Poly for Formula X. For both of Formulas II and X, the preferred number of carbodiimide groups designated by p and k respectively is from 2 to 100, preferably from 2 to 50, more preferably from 2 to 10, most preferably 2 to 5. The foregoing preferred L groups (non-polymeric L groups for Formula II) provide the molecular size for these preferred versions of Formula II. For Formula X, the preferred Poly is polyamide formed of hexane diamine and adipic acid with the pendant K groups formed from 3-aminopropyl-1,6-hexane diamine. Based upon factors such as but not limited to the number of L groups, the size of Poly and the number of carbodiimide groups the weight average molecular weight of the linker may range from 0.5 KDa to about 500 KDa, preferably about 0.5 KDa to about 400 KDa, more preferably about 0.5 KDa to about 10 KDa, most preferably about 0.5 KDa to about 3 KDa to 5 KDa.

The binder and linker molar concentrations and their relative level of functional groups in the film forming composition deliver a ratio of carboxylic acid to carbodiimide groups. In some embodiments of the film forming composition, the binder provides a number of carboxylic acid groups equal to the number of carbodiimide of the linker. In preferred embodiments of the film forming composition, the linker provides an excess number of carbodiimide groups relative to the number of carboxylic acid groups of the binder. This ratio enables carbodiimide addition of the linker with the amine groups of the small molecule of the pretreatment composition. In more preferred embodiments of the film forming composition, the ratio of linker carbodiimide groups to binder carboxylic acid groups may range from about 50:1 to 1.2:1, preferably about 30:1 to 2:1, more preferably about 25:1 to 2.5:1, especially more preferably about 20:1 to about 3:1, most preferably about 20:1 to about 10:1.

Pre-Treatment Composition

The significant remanence, wear-fastness and resistance to environmental attack of the color coating on keratin fibers according to aspects of the invention may be developed through interaction between and among any one or more of the components of the film forming composition, the pre-treatment composition and the keratin fibers, preferably anagenic hair. The interactions are complex and involve cooperation of binder and pretreatment small molecule/PEI-type components through covalent bonding, hydrogen bonding, dipolar interaction, molecular intertwining. The interactions also are believed to involve at least in part covalent bonding and non-covalent interactions between and among the keratin fiber surfaces and the components of the pre-treatment composition and the components of the film forming composition. Embodiments of the pre-treatment composition may comprise organosilicone and/or silicone small molecules that incorporate alkoxysilyl groups and preferably also amine groups. Additionally, an embodiment of the pre-treatment composition may comprise an amine polymer such as polyethylene imine (PEI) however, preferred embodiments are the small molecules.

The organosilicone and/or silicone small molecules of the pre-treatment composition preferably have a weight average molecular weight of from about 100 Da to about 1 KDa.

Embodiments of the pretreatment compositions as small molecules comprise silicon cores of from 1 to 6 silicon atoms, preferable 1 to 3 silicon atoms, more preferably 1 or 2 silicon atoms and most preferably one silicone atom. Alternatively, the small molecules comprise an organic core of 1 to 10 carbons or a small number of repeat monomeric units. The silicone and organic core small molecule embodiments of the pre-treatment composition may also comprise one or more organoamine groups and one or more alkoxysilyl groups. The number of amine groups and alkoxy silyl groups present in the small molecule will depend upon the kinds of inter molecular connections desired for the pre-treatment composition. In particular, the small molecules may contain at least one and preferably two organoamine groups for optional covalent bonding with the CDI component of the film forming composition and at least polar and electrostatic interactions with such polar groups as carboxyl and amide groups of the keratin protein at the surfaces of the keratin fibers. In particular, the small molecule will also contain at least two and preferably at least three alkoxysilyl groups. The alkoxysilyl groups may provide covalent silicon-oxygen-carbon bond formation with monomeric units of keratin protein which carry pendant hydroxyl groups, such as serine, threonine and tyrosine. The alkoxysilyl groups may also interact with keratin amino acid moieties carrying carboxyl side chains, such as aspartic acid and glutamic acid. In this instance, the intermediate carboxylsilyl group may further combine with amine groups from any source to form amide linkages. The alkoxysilyl groups may also interact with cysteine to form a thio analog silicon-sulfur-carbon bond formation or interact by dipolar and/or ionic interaction. The alkoxysilyl groups may also interact with alkoxysilyl counterparts of the linker when they are present on the linker.

The small molecule embodiment of the pre-treatment composition may be conceptualized as Formula III:

[(H₂N)—((CH₂)_(m)—NH)_(o)—(R¹⁴)_(n))]_(a)—[RO_(t)Me_(3-t)Si—O]_(b)—(—SiMe₂-O)_(p)—(—SiMeOR—O)_(q)—[(—SiMe_(2-r′)[(CH₂)_(m′)—NH₂]_(r)—O]_(s)-[A]_(c)-[(—SiMeMe_(2-v)-O]_(u)—SiMe_(3-t)OR_(t)   Formula III

Formula III incorporates several additional functional groups with the organosilyl small molecules having the alkoxysilyl functional group. Some of these are: a) organoamine groups, b) additional alkoxysilyl groups, mercapto groups, multialkylamino groups, α,β unsaturated alkenoyloxy groups such as (meth)acryloyl, ureido, dithio, alkyl, aromatic and similar groups as described by A.

To accomplish these variations, Group A may be a divalent group including dithio, diazo, urethanyl, ureido, or C1-C6 alkylenyl connecting left and right sections of the small molecule, or Group A may be a terminal group including C1-C14 alkyl, C1X-C14X alkyl wherein X is N, S or O and X may be in-chain or terminal so as to provide an aminoalkyl, a mecapto alkyl or hydroxyalkyl group or the corresponding groups with the heteroatom in the alkyl chain, C1-C6 alkoxy, C7-C14 arylalkyl, C6X-C14X heteroarylalkyl with X as N, S or O; C1-C6 alkylenyl(meth)acrylate or C1-C6 alkylureido.

The R groups and designators have the following definitions. The R and R¹⁴ groups are alkyl groups. R provides the alkyl group of the alkoxysilyl group and may be methyl or ethyl. R¹⁴ is a C1-C6 alkylenyl group.

Designators m and m′ may be an integer of 1 to 3. Designators o, n, b, r, s, c, u may be zero or 1. Designator a may be zero, 1 or 2. Designator v may be zero, 1 or 2 such that when a is 2, v is 2 and when a is 1, v is 1 and when a is zero, v is 1 or zero. Designator t may be 1 to 3. Designators p and q independently may be zero or an integer of 1 to 6. Designator t may be zero or an integer 1-3.

For Formula III, the designators a as zero and b as 1 describe the small molecule with alkoxysilyl groups at both termini. These same designators with a as 1 and b as zero describe a small molecule with an alkoxysilyl group at one terminus and an organoamine group at the other terminus. The designators m, o, n and m′ determine the size of the organoamine group and the number of secondary amines present. The designator p determines the number of dimethylsiloxane units in the small molecule. The designators q and s determine whether or not the small molecule has pendant alkoxysilyl groups (designator q) and/or has pendant organoamine groups (designator s).

The group A may or may not be present depending on whether c is 1 or zero. Group A may be a divalent group including dithio, diazo, urethanyl, ureido, or C1-C6 alkylenyl connecting left and right sections of the small molecule. Alternatively, group A may be a terminal group including C1-C14 alkyl, C1X-C14X heteroalkyl with X as N, S or O either in chain or as a terminus such that this group may be w-aminoalkyl, w-mercaptoalkyl, w-hydroxyalkyl or the alkyl with N, S or O in the alkyl chain, C1-C6 alkoxy, C7-C14 arylalkyl, C6X-C14X heteroarylalkyl with X as N, S or O, C1-C6 alkylenyl(meth)acrylate or C1-C6 alkylureido when c is 1 and a, b, p, q and s are all zero. In this instance, u may be 1 and v is 1 so that the terminal A group is bound to a dimethylsiloxane chain terminated by an alkoxysiloxane group. Alternatively, u may be zero so that the A group is bound to the silicon of the alkoxysilyl terminus. Finally, with A as an alkylenyl, c as 1, b, p, q, s and v as zero and a as 2, the small molecule has two aminoalkyl groups bonded to A as alkylenyl which in turn may be bonded to a dimethylsiloxane unit (u as 1) or to an alkoxysilyl terminus (u as zero).

Exemplary embodiments of the small molecule component of the pre-treatment composition include but are not limited to APTES, triethoxysilylamine, 1,1,1-triethoxy, 2,2-dimethyl-2-aminodisiloxane, aminoalkylmonoethoxydimethylsilane, mercaptoalkyltriethoxysilane, aminoalkyldiethoxymethylsilane and aminoalkyltriethoxysilane with 1 to 6 carbons in each alkyl group, preferably 2 or 3 carbons;

Another exemplary embodiment is (EtO)₃Si—O-(Me₂SiO)_(n)—SiMe₂(CH₂)_(m)NH₂ with n as 1 to 3 and m as 2 to 6, preferably 2 or 3.

Yet another exemplary embodiment is (EtO)₃Si—O-(Me₂SiO)_(n)—(SiOMe_(2-t)((CH₂)_(o)NH₂)_(q)—SiMe₂(CH₂)_(m)NH₂ with n as 1 to 3, t as 1 or 2, o as 1 to 6 preferably 2 or 3, q as zero, 1 or 2 and m as 2 to 6, preferably 2 or 3.

An additional exemplary embodiment is (EtO)₃Si—O-(Me₂SiO)_(n)—(SiOMe_(2-t)((CH₂)_(o)NH₂)_(q)—(CH₂)_(r)—O—SiMe₂(CH₂)_(m)NH₂ with n as 1 to 3, t as 1 or 2, o as 1 to 6 preferably 2 or 3, q as zero, 1 or 2, r as 1-6, and m as 2 to 6, preferably 2 or 3. This embodiment provides A as an alkylenyl group.

When o, p, q, s, c and u are zero, a is 1, n is 1, R¹⁴ is propyl, R is ethyl and t is 3, the small molecule is aminopropyl triethoxy silane having the acronym APTES.

When m is 3, o and n are each 1; R¹⁴ is propyl; b, p, q, s and c are zero, R is ethyl and t is 3, the small molecule is N-(3-aminoprop-1-yl)-3-aminoprop-1-yl triethoxysiloxane.

When m and o are zero, n is 1, R¹⁴ is propyl, a is 2; b, p, q, s and u are all zero; c is 1, A is CH and t is 3, the small molecule is di(aminopropyl) methyl triethoxysilane. With this same configuration but with c as zero and u as 1, the small molecule is di(aminopropyl)methylsilyloxytriethoxysiloxane which is (H₂N(CH₂)₃)₂SiMeOSi(OET)₃.

Table 10 provides a listing of appropriate amino alkoxy silane compounds as small molecules of the pre-treatment composition. Some of the Table 10 compounds are not covered by Formula III but nevertheless are included as small molecules for the pretreatment composition.

TABLE 10 ALKOXYSILANE PRETREATMENT SMALL MOLECULES HEXYLTRIETHOXYSILANE OCTYLTRIETHOXYSILANE 3-ETHYLHEXYLTRIETHOXYSILANE 4-AMINO-3,3-DIMETHYLBUTYLTRIMETHOXYSILANE 4-AMINOBUTYLTRIETHOXYSILAN N-(2-AMINOETHYL)-3-AMINOPROPYLTRIETHOXYSILANE, 3-(m-AMINOPHENOXY)PROPYLTRIMETHOXYSILANE m-AMINOPHENYLTRIETHOXYSILANE, m-AMINOPHENYLTRIMETHOXYSILANE, 3-AMINOPROPYLTRIETHOXYSILANE 3-AMINOPROPYLTRIMETHOXYSILANE 3-AMINOPROPYLTRIS(METHOXYETHOXYETHOXY)SILANE, 11-AMINOUNDECYLTRIETHOXYSILANE 2-(4-PYRIDYLETHYL)TRIETHOXYSILANE 2-(2-PYRIDYLETHYL)TRIMETHOXYSILANE N-(3-TRIMETHOXYSILYLPROPYL)PYRROL 3-AMINOPROPYLSILANETRIOL 4-AMINO-3,3-DIMETHYLBUTYLMETHYLDIMETHOXYSILANE 3-AMINOPROPYLMETHYLDIETHOXYSILANE 1-AMINO-2-(DIMETHYLETHOXYSILYL)PROPANE, 3-AMINOPROPYLDIISOPROPYLETHOXYSILANE 3-AMINOPROPYLDIMETHYLETHOXYSILANE (AMINOETHYLAMINOMETHYL)PHENETHYLTRIMETHOXYSILANE, N-(2-AMINOETHYL)-3-AMINOPROPYLTRIMETHOXYSILANE, N-(2-AMINOETHYL)-3-AMINOPROPYLTRIMETHOXYSILANE, N-(6-AMINOHEXYL)AMINOMETHYLTRIETHOXYSILANE N-(6-AMINOHEXYL)AMINOPROPYLTRIMETHOXYSILANE N-(2-AMINOETHYL)-11-AMINOUNDECYLTRIMETHOXYSILANE N-3-[(AMINO(POLYPROPYLENOXY)]AMINOPROPYLTRIMETHOXYSILANE N-(2-N-BENZYLAMINOETHYL)-3-AMINOPROPYLTRIMETHOXYSILANE, N-(2-AMINOETHYL)-3-AMINOPROPYLSILANETRIOL, N-(2-AMINOETHYL)-3-AMINOPROPYLTRIMETHOXYSILANE- PROPYLTRIMETHOXYSILANE N-(2-AMINOETHYL)-3-AMINOISOBUTYLMETHYLDIMETHOXYSILANE N-(2-AMINOETHYL)-3-AMINOPROPYLMETHYLDIETHOXYSILANE N-(2-AMINOETHYL)-3-AMINOPROPYLMETHYLDIMETHOXYSILANE N-(2-AMINOETHYL)-3-AMINOISOBUTYLDIMETHYLMETHOXYSILANE, (3-TRIMETHOXYSILYLPROPYL)DIETHYLENETRIAMINE 3-(N-ALLYLAMINO)PROPYLTRIMETHOXYSILANE, n-BUTYLAMINOPROPYLTRIMETHOXYSILANE t-BUTYLAMINOPROPYLTRIMETHOXYSILANE (N-CYCLOHEXYLAMINOMETHYL)METHYLDIETHOXYSILANE (N-CYCLOHEXYLAMINOMETHYL)TRIETHOXYSILANE, (N-CYCLOHEXYLAMINOPROPYL)TRIMETHOXYSILANE (3-(N-ETHYLAMINO)ISOBUTYL)METHYLDIETHOXYSILANE (3-(N-ETHYLAMINO)ISOBUTYL)TRIMETHOXYSILANE N-METHYLAMINOPROPYLMETHYLDIMETHOXYSILANE N-METHYLAMINOPROPYLTRIMETHOXYSILANE N-PHENYLAMINOMETHYLTRIETHOXYSILANE N-PHENYLAMINOPROPYLTRIMETHOXYSILANE N,N-BIS(2-HYDROXYETHYL)-3-AMINOPROPYLTRIETHOXYSILANE, BIS(3-TRIMETHOXYSILYLPROPYL)-N-METHYLAMINE (N,N-DIETHYLAMINOMETHYL)TRIETHOXYSILANE (N,N-DIETHYLAMINOMETHYL)TRIMETHOXYSILANE, 3-(N,N-DIMETHYLAMINOPROPYL)AMINOPROPYLMETHYLDIMETHOXYSILANE N,N-DIMETHYL-3-AMINOPROPYLMETHYLDIMETHOXYSILANE N-METHYL-N-TRIMETHYLSILYL-3-AMINOPROPYLTRIMETHOXYSILANE TRIS(TRIETHOXYSILYLMETHYL)AMINE, TRIS(TRIETHOXYSILYLPROPYL)AMINE 1-[3-(2-AMINOETHYL)-3-AMINOISOBUTYL]-1,1,3,3,3-PENTAETHOXY-1,3- DISILAPROPANE, BIS(METHYLDIETHOXYSILYLPROPYL)AMINE, BIS(3-TRIETHOXYSILYLPROPYL)AMINE N,N′-BIS[3-(TRIETHOXYSILYL)PROPYL]UREA, 1,11-BIS(TRIMETHOXYSILYL)-4-OXA-8-AZAUNDECAN-6-OL, BIS(3-TRIMETHOXYSILYLPROPYL)AMINE, N,N′-BIS[(3-TRIMETHOXYSILYL)PROPYL]ETHYLENEDIAMINE BIS(3-TRIMETHOXYSILYLPROPYL)-N-METHYLAMINE N,N′-BIS(3-TRIMETHOXYSILYLPROPYL)THIOUREA, N,N′-BIS(3-TRIMETHOXYSILYLPROPYL)UREA, N-n-BUTYL-AZA-2,2-DIMETHOXYSILACYCLOPENTANE 1-ETHYL-2,2-DIMETHOXY-4-METHYL-1-AZA-2-SILACYCLOPENTAN (1-(3-TRIETHOXYSILYL)PROPYL)-2,2-DIETHOXY-1-AZA-2- SILACYCLOPENTANE, BIS(3-TRIETHOXYSILYLPROPYL)CARBONATE 2-(3,4-EPOXYCYCLOHEXYL)ETHYLTRIETHOXYSILANE 5,6-EPOXYHEXYLTRIETHOXYSILANE HYDROXYMETHYLTRIETHOXYSILANE BIS(TRIETHOXYSILYL)METHANE 1,8-BIS(TRIETHOXYSILYL)OCTANE 1,2-BIS(TRIMETHOXYSILYL)ETHANE BIS(TRIMETHOXYSILYLETHYL)BENZENE, N-PHENYLAMINOMETHYLTRIETHOXYSILANE N,N-BIS(2-HYDROXYETHYL)-3-AMINOPROPYLTRIETHOXYSILANE, N-(2-N-BENZYLAMINOETHYL)-3-AMINOPROPYLTRIMETHOXYSILANE HYDROCHLORIDE, METHACRYLOXYPROPYLTRIETHOXYSILANE (METH)ACRYLOXYPROPYLTRIMETHOXYSILANE (3-ACRYLOXYPROPYL)METHYLDIMETHOXYSILANE, (AMINOETHYLAMINOMETHYL)PHENETHYLTRIMETHOXYSILANE, UREIDOPROPYLTRIETHOXYSILANE UREIDOPROPYLTRIMETHOXYSILANE Ω-MERCAPTOALKYLTRIMETHOXY OR TRIETHOXYSILANE, ALKYL = C3-C12

Preferred alkoxysilane small molecules of the pretreatment composition from Table 10 include:

a) trimethoxysilyl propyldiethylene triamine (SCA); b) trimethoxysilyl propyl (meth)acrylate ester (MEMO); c) aminopropyl triethoxysilane (APTES); d) octyl triethoxysilane (OCTEO); e) propyltriethoxysilane (PTEO); f) ureidopropyl trimethoxysilane (UREIDO); g) phenylsilane (PHS); h) tetraethoxy silane (TEOS); i) 3-aminopropylsilyltriol; j) 3-mercaptopropyltriethoxy or trimethoxy silane; k) 3-glycydyloxypropyltrimethoxysilane (GLYEO); l) N-(2-aminoethyl)-N′-(3-(trimethoxysilyl)propyl)ethylenediamine (TRIAMO).

Praeparatur and Fundamenta Techniques

A typical procedure for coloration of anagenic hair may involve application of a permanent oxidative dye formulation or may involve semi-permanent application of a direct dye or may involve temporary coloration that can be removed by a single mild shampoo washing. These three techniques for hair coloration traditionally are applied to anagenic hair without a prior wash of the anagenic hair. The presence of sebum, fatty acids (F layer), natural oils, sweat residue, mineral excretion from skin pores are traditionally regarded as helpful in the practice of these coloration techniques. Of course, if the anagenic hair also contains dirt particles, it is usually combed thoroughly to remove dirt debris but the natural oils, secreted minerals, sebum, fatty acids and the like remain.

It is expected therefore that the remanent results demonstrated by formation of a color coating according to the invention on a treated or untreated tress would also be demonstrated by formation on anagenic hair of a color coating according to the invention. In contrast to this expectation, and as shown by the mimic tress experiments described below, a color coating formulated onto anagenic hair such as hair on the scalp of a female hair model does not display long-lasting remanence. The hue, intensity and shade of the color coating on anagenic hair such as that of a model rapidly decreases with each shampooing and by 3 shampoo washes or less, the color coating is gone, especially for color coating on the root portion of anagenic hair.

In contemplation of these results, it was realized that treated and untreated tresses fundamentally differ in at least one respect from anagenic hair. The treated and untreated tresses which are the typical universal substrate for keratin fiber experimentation are not connected to hair follicles and do not receive continuous secretions of sebum, natural oils and fatty acid as well as sweat and mineral secretions from adjacent skin pores. This realization led to experimentation to improve remanence on anagenic hair by converting it to hair like that of treated and untreated tresses. These attempts involved initial removal of sebum, natural oils, fatty acid secretions, sweat and mineral secretions by detergent washing as is usually performed on cut hair being prepared for treated tresses. These attempts also failed. Subsequent body secretions appurtenant to the hair on the scalp of hair models were found to continue circumvention of the remanence result experienced with treated and untreated tresses.

Continued research has led to a combination of aspects that have enabled development of a color coating on anagenic hair that displays remanence similar to that displayed by treated and untreated tresses. These aspects include at least the techniques of Praeparatur and Fundamenta in combination with the Pretreatment Composition with small molecules described above.

Prepareratur Technique

Substantially complete initial removal of sebum coating the surfaces of anagenic hair delivers a bare hair strand surface exposing the microscopic topographic variability provided by keratin protein at this surface. To obtain such keratin fiber priming, a Praeparatur technique is applied. The Praeparatur technique may be any priming operation that removes sebum from the surfaces of keratin fibers. Exemplary Praeparatur techniques include use of one or more applications of one or more applications of a non-conditioning or substantially non-conditioning surfactant which is free of conditioning actives or substantially free of conditioning additives such as silicones, e.g., amodimethicone, or cetrimonium chloride and polymers such as the polyquaternium versions of cellulose and guar gum derivatives. This technique calls for one or more applications of the surfactant in an aqueous or aqueous-alcoholic medium with optional agents for ionicity and pH control in which the kinds and concentrations of components are adjusted to achieve the desired priming effect. The technique involves use of a mild to moderate aqueous composition of an anionic, non-ionic, amphoteric or zwitterionic surfactant at a concentration beginning at about 2 wt % and escalating to about 30 wt %, preferably up to about 25 wt %, more preferably up to about 10 wt % to about 25 wt % relative to the total weight of the composition. The surfactant composition may also include agents for adjustment of viscosity and ionicity and optional adjustment of pH from acidic to neutral to basic. The surfactant composition may begin with a mild surfactant such as a non-ionic or its mixture with other surfactants and may escalate to higher concentrations of anionic surfactant. A preferable surfactant is an anionic surfactant displaying amphiphilic properties such as an alkali metal salt of a C8-C16 alkyl carboxylate, phosphate, sulfonate, sulfate in which the strength of amphiphilic character increases from carboxylate to sulfate. The initial nonionic surfactant used may be followed by a stronger anionic surfactant and then by a solubilizing anionic surfactant having either a PEG group such as PEG-2 to PEG-20, preferably PEG-2 to PEG-5 for increased hydrophilicity or a PPG group such as PPG-2 to PPG-5 for increased lipophilicity inserted between the anionic head and the alkyl lipophilic tail of the anionic surfactant. Yet stronger solubilizing media may be formulated by increasing the ionic strength and adjusting the pH. Ionicity builders such as alkali metal sulfates, carbonates, phosphates, nitrates and/or xylene sulfonate may be added. The nature of the medium may also be adjusted to provide organic solvents that are capable of solubilizing oils and sebum. Included are C2 to C8 alcohols, preferably isopropanol, isobutanol, tert-butanol and neohexanol. This escalating priming treatment is designed to escalate in mild stepwise fashion so as to avoid overchallenge of the hair.

This escalating priming treatment may be coupled with mechanical agitation such as by a fine tooth comb and/or by a sound vibration such as with a ultrasound device operating at least at 20K Hertz. The mechanical and/or sound vibration can agitate the anagenic hair strands to loosen coatings of sebum, natural oils and secreted sweat and minerals. The ultrasound device may be designed as a fine tooth comb, the teeth of which vibrate to produce the ultrasound. Alternatively, the ultrasound device may be a hand-held generator held in combination with a fine tooth comb which is run through the anagenic hair under the above described priming conditions.

Fundamenta Technique

The Praeparatur technique often will be sufficient to prime a fiber surface and allow adherence of the pretreatment small molecule with surface exposed protein. However, application of the Praeparatur technique to anagenic hair may not fully prime the bare surface protein of keratin fibers. In such instances, application of the Fundamenta technique may accomplish deep cleaning of the keratin fibers such as anagenic hair. The Fundamenta technique may be applied as a follow-on to use of the Praeparatur technique or applied without prior use of the Praeparatur technique or may be applied first with subsequent use of the Praeparatur technique. The Fundamenta technique structurally deep cleans the surface topography and chemical make-up of the surfaces of keratin fibers and removes the F layer coating on the keratin fibers. The technique also may but not necessarily adjust the topography of the fiber surfaces so as to enable better access of the pretreatment small molecules to the fiber surfaces. This technique may be accomplished by any deep cleaning operation that removes the F layer and deep cleans the keratin fiber surfaces. Exemplary activities include use of one or more of cold plasma discharge, surface oxidizer such as but not limited to ozone, peroxide and/or persulfate and/or a form of chlorite treatment and/or an alkali phase transfer tenside (PETT) such as a multi alkyl ammonium halide, examples of which are C2-C20 alkyl trimethyl ammonium chloride (CTAC) or bromide (CTAB) such as choline halide, cetyl trimethylammonium halide or stearyl trimethylammonium halide.

The cold plasma treatment may be accomplished by passing partially ionized gas over anagenic hair or mimic tresses. Cold plasma is a non-equilibrium atmospheric plasma of a gas such as air or oxygen and/or nitrogen having an effective gas temperature approximating ambient temperature, while the electron temperature may be much higher. The gas is passed between dielectric coated electrodes at a high AC voltage potential difference, or through an RF field. The electromagnetic field dislodges some electrons from the gas atoms to produce a cascade of ionization process which lead to the cold plasma stream. An example is an ozone generator which passes air through a high voltage spark discharge. Cold plasma generators are commercial devices designed for production of ambient temperature (cold) plasma. The plasma is transported through a flexible tube to a nozzle. The nozzle through which the plasma stream flows may be passed over the keratin fibers to accomplish plasma treatment. A typical treatment of a mimic hair tress involve passing the nozzle with flowing plasma over the keratin fibers for approximately 1 to 5 minutes, preferably about 1 to about 3 minutes.

The alkali phase transfer tenside treatment is accomplished by washing anagenic hair and/or mimic tresses with an aqueous solution of phase transfer tenside with an alkaline base or a nucleophile such as an alkoxide. A phase transfer tenside (PETT) generically is a C2-C20 multi-alkyl ammonium halide such as choline or preferably a C12-C20 alkyl trimethyl ammonium chloride or bromide, more preferably cetyl (C16) and/or stearyl (C18) trimethyl ammonium bromide (CTAB). The PETT may be formulated as a 0.1 wt % to 25 wt % aqueous solution. An alkali or thiol aqueous solution (basic alkali pH>10, basic thiol pH>7) of the PETT may be applied to a mimic tress or anagenic hair and massaged through the hair strands either by hand or by brush for a period of 5 to 30 minutes, preferably 5 to 15 minutes to obtain PETT treatment. Thereafter, the tress or anagenic hair, which is substantially saturated with aqueous, basic PETT, is repeatedly rinsed with shampoo in acidic medium to remove the PETT solution.

The surface oxidizer treatment is accomplished by exposing anagenic hair or mimic tresses to a dilute oxidizer solution. The oxidizer solution may be formulated as an aqueous solution of a persulfate, hypochlorite, peroxide or ozone typically at a concentration of from about 0.5 wt % to about 10 wt %, preferably about 0.5 wt % to about 5 wt %, more preferably about 0.5 wt % to about 2 wt %. The oxidizer solution can be at an elevated pH, due to the presence of ammonia or MEA or sodium silicate or metasilicate. The oxidizer solution is applied to a mimic tress or anagenic hair and massaged through the hair strands either by hand or by brush for a period of from 10 seconds to about 5 minutes, preferably about 10 seconds to about 1 to 2 minutes. Thereafter the tress or anagenic hair, which is substantially saturated with oxidizer solution, is repeatedly rinsed with water to remove the oxidizer solution.

The basic and/or nucleophilic medium for use with any of the Fundamenta treatment may be any that does not swell the hair strands but will dissolve the resulting free 18-methyleicosanoic acid (F-layer acid). An example of such a medium is t-butoxide in t-butanol or an alkyl or aromatic thiol such as hexyl thiol or thiophenol in acetone.

It is believed that the Praeparatur and Fundamenta techniques enable intimate interaction of the pretreatment small molecule and the surfaces of anagenic hair strands. The Praeparatur and Fundamenta techniques prime and deep clean the hair strand surfaces to remove at least sebum and the F layer so that the small molecule is better able to adhere intimately with and within the peaks, shoulders, and valleys of the surfaces of the keratin fibers as well as with the microscopic topography involving the keratin protein in at the fiber surfaces. This ability of the small molecule is also related to its small size and reactive energy. As mentioned previously, the presence of the sebum and fatty acid f layer surrounding the surfaces of keratin fibers of anagenic hair presents a surprising problem with respect to treated and untreated tresses. The Praeparatur and Fundamenta techniques practiced in combination with the application of the pretreatment composition with small molecules enable this intimate adherence with the microscopic topography of the protein at the surfaces of the keratin fibers. Once in place, the small molecule embodiments are readily able to self-condense to form polysiloxane three dimensional networks in intimate adherence with these keratinaceous surfaces. Subsequent covalent interactions between remaining reactive groups of the condensed small molecule embodiments and the binder component of the film forming composition are believed to extend the three dimensional network. Because of the microscopic topographic adherence of the three dimensional network of condensed small molecules to the keratin surface proteins, it is believed that continued sebum and fatty acid secretions onto the keratin fiber shafts are unable to work their way (worm) underneath the network and dislodge it. The network, in turn is intimately interconnected with the three dimensional network formed through condensation of the binder of the film forming composition. The cooperation of these networks inter-adhered with the keratinaceous surfaces is believed at least in part to provide significant remanence of anagenic hair. These aspects according to the invention are believed to produce at least in part qualities and characteristics of the color coating on the keratinaceous surfaces and especially on the surfaces of hair strands of anagenic hair.

Medium

When applied to keratin fibers, the media of the film forming composition and pretreatment composition embodiments of the invention may be an organic compound that is capable of being intimately mixed or preferably will form a solution with a minor amount of water. The preferred media comprise embodiments of alcoholic solvents such as an alkyl alcohol of 1 to 6 carbons with no intentionally added water. Included are methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, n-butanol, isobutanol, pentanol, neopentanol, isopentanol and n-hexanol. Preferred organic alcohols include ethanol, n-propanol, isopropanol, n-butanol and isobutanol and pentanol. More preferred organic alcohols include isopropanol and isobutanol. The alcoholic solvent may be intentionally combined with water in amounts up to about 10 weight percent, preferably up to about 8 weight percent, more preferably up to about 5 weight percent and most preferably up to about 4 or 5 weight percent relative to the total weight of the media. It is recognized that alcohol solvents absorb water from the atmosphere so that an alcoholic solvent with no intentionally added water may contain a slight amount of water. Although it is not a limitation of the invention, it is believed that the presence of water facilitates the condensation of the alkoxysilyl groups to silyloxysilyl groups by hydrolyzing the alkoxy groups to hydroxyl groups. Additionally and optionally, for management of the acid-CDI reaction, control of the pH toward basic by use, for example of an amine such as trimethyl or triethyl amine or ammonia in a minor concentration such as but not limited to about 0.1 wt % to about 5 wt % relative to the medium weight may be added to the aqueous alcohol medium for the film forming composition to moderate this reaction.

Additionally, the aqueous-organic medium for the pretreatment composition may include a minor amount of acetic acid, such as from about 0.1 wt % to about 5 wt %, preferably from about 0.1 wt % to about 3 wt %, more preferably from about 0.1 wt % to about 2 wt % relative to the total weight of the medium. Alternatively, a 90%-95% aqueous medium with ethanol and acetic acid may be used for the pretreatment composition. The presence of acetic acid facilitates hydrolysis of the alkoxysilyl groups to hydroxysilyl groups and renders the small molecule of the pretreatment composition more soluble in water. When acetic acid is present in the aqueous-alcoholic pretreatment composition, the lifetime of the small molecule is on the order of at least a few hours. Consequently, this option for application of the pretreatment composition is typically conducted in small batches which are mixed and immediately used. The medium for the pretreatment composition may also include a balance among the amounts of alcohol, water and acetic acid present relative to the identity of the small molecule present. In some instances, the acid and/or water concentrations may be greater than in others. Determination of appropriate and/or optimum ratios of concentrations for the individual small molecules, the choice and amount of medium and the presence and amount of acid or base are within the ordinary experimental ability and technique of the laboratory technician.

The binder and linker of the film forming composition and the pretreatment composition are maintained separately until use. Packaging each in separate containers serves this purpose. Each of the binder, linker and small molecule of the pretreatment composition may be maintained in a medium that does not interact with the reactive groups. Suitable media for the binder and linker are non-aqueous organic solvents such as but not limited to the alcohols mentioned above, preferably isopropanol and isobutanol or liquid hydrocarbon or silicone solvents. The media for separately maintaining the binder, linker and small molecule should not include water or agents that would hydrolyze alkoxysilyl groups or interact with the carbodiimide groups. Typically, the binder, linker and small molecule preparations for storage may be formulated as ready to use concentrations or may be concentrates which may be diluted with appropriate media to prepare them for use or may be ready to use concentrations for application to keratin fibers.

When the film forming composition and the pretreatment composition are prepared for application to keratin fibers, they may be formulated with a single phase alcohol or alcohol medium as described above or may be formulated as a two phase aqueous medium with water or water-alcohol as the continuous phase and a water or water-alcohol immiscible organic liquid as the discontinuous phase. The continuous phase may carry water soluble constituents while the discontinuous phase may carry constituents such as those of the film forming composition and the alkoxysilyl small molecule of the pretreatment composition that would react with water. The discontinuous, non-aqueous phase will tend to isolate such compounds from degradation by water. Preferably, in situations when water is to be part of a medium but one or more of the components of the film forming composition and pretreatment composition are sensitive to water, the film forming composition and pretreatment composition may be maintained in a non-aqueous environment until they are ready for dressing on keratin fibers. At the application stage, a single phase or two phase medium may be prepared as appropriate.

The polarity and protonic character of the medium are important for control of the several reactions that occur when the components of the film forming composition and pretreatment composition are combined. These reactions include the reactive termini/pendant alkoxysilyl groups which undergo alkoxysilyl condensation to form silyloxysilyl linkages as well as the acid-CDI addition. Preferably, the medium for application of the film forming composition and the pre-treatment composition is polar and can support the condensation and addition reactions. For both of the film forming composition and pretreatment composition, isopropanol or isobutanol as described above is appropriate. The application media may be combined with the separately stored concentrates of binder, linker and small molecule and the media of the stored concentrates preferably will be at least partially to substantially miscible with the application media.

The medium may be independently present in each of the film forming composition and the pretreatment composition in an amount ranging from about 0.1% to about 99% by weight, such as from about 1% to about 98% by weight, for example ranging from 50% to 95% by weight relative to the total weight of which of the film forming composition and pretreatment composition is under consideration.

Viscosity, Compositional Constituent Concentrations

The viscosities of the film forming composition and pretreatment composition function to hold them in place on the keratin fibers while the color coating is formed. The viscosity substantially avoids free translational flow of these compositions. Free translation flow would cause the compositions to rapidly run and drip off the surfaces of the hair strands. Nevertheless, the viscosity is not so high that it will not undergo self-leveling to coat the keratin fibers substantially uniformly. Appropriate viscosity of the compositions is the result of the interaction of the various constituents of the film forming and pretreatment compositions, their concentrations, the pigment microparticles, and as appropriate, an optional viscosity control agent, an optional suspending agent and an optional thickening agent.

Generally, the viscosity of the film forming and pretreatment compositions may range from about 0.001 to about 2000 Pa s⁻¹. Viscosity measurements are carried out on a controlled stress rheometer e.g. Using an AR2000 type manufactured by TA Instruments, or equivalent instrument. A 6 cm flat acrylic cross hatched parallel plate geometry (TA item 518600.901) and a stainless steel cross hatched base plate (TA item 570011.001) are used. The rheometer is prepared for flow measurements as per standard manufacturer procedure. The parallel plate geometry gap is set to 1000 microns. The flow procedure is programmed to the rheometer with the following conditions: continuous stress ramp 0.1-300 Pa over 2 minutes at 25° C., including 250 measurement points in linear mode. The product is loaded into the geometry as per standard procedure and the measurement commences at 5 min after the mixture preparation. Shear stress value at 10 sec-1 shear rate is obtained from the shear stress vs. shear rate curve, and the corresponding viscosity is calculated by dividing the obtained shear stress by 10.

The concentration of the binder and linker constituents in the film forming composition and the concentration of the small molecule constituent in the pretreatment composition may each independently range from about 0.1% to about 90%, preferably about 1% to about 40%, more preferably about 2% to about 30%, most preferably about 2% to about 15% by weight relative to the total weight of the composition. As discussed above, the viscosity is managed so that the film forming and pretreatment compositions will not run off the surfaces of strands of hair yet will level and flow to substantially coat those surfaces. Development of appropriate viscosity in part by management of the concentrations of the constituents of the film forming and pretreatment compositions can be experimentally determined by routine methods such as formulation of several samples of differing concentrations of constituents in these compositions, coating those samples on a hair tress and observing the flow, spread and leveling of the composition on the hair strands.

The film forming and pretreatment compositions can be applied simultaneously, sequentially or in pre-combined form to keratin fibers such as a hair tress using the coloring procedure described herein afterwards. The top of the hair strand, where it is bound together is fixed such that the hair is aligned vertically downwards. After a 5 minute dwell time it is observed if any and how much product has dripped from the hair tress. The results obtained from the several samples can be plotted against flow time and leveling time to determine an appropriate concentration or range of concentrations of the constituents of the film forming and pretreatment compositions.

The extent of linking between and among the reactive constituents of the film forming and pretreatment compositions may be controlled by manipulation of ratios, amounts present and concentrations as well as by physical means as described above so that the mechanical and chemical properties of the color coating as described herein are preserved. These properties include ability to adhere to hair strands, ability to maintain flexibility and free flowing character of the hair, ability to provide remanence, avoidance of stickiness and avoidance of clumping.

The glass transition temperatures of the crosslinked binder and linker of the film forming composition and the polymerized small molecule of the pretreatment composition in part contribute to the flexibility, strength, hardness and similar qualities of the color coating on the keratin fiber surfaces. The glass transition temperatures of these embodiments preferably are well below ordinary minimum environmental temperatures such as −30° to −100° C. The glass transition temperature or T_(g) determines the solid-solid transition of the polymer from a hard glassy material to a soft rubbery material. For the purposes of the color coating on keratin fibers, the soft, rubbery, elastic state is the state to be achieved. If the T_(g) of the color coating is too high, such as above ambient temperature the color coating on the keratin fibers will be stiff and inflexible. This is an undesirable result. The coating should be soft, flexible, elastic and unnoticeable to touch and sight yet should not flake, break-up or otherwise release from the keratin fiber, and especially from anagenic hair, when stroked by a hand or brushed with a brush. The Tg of a color coating can be measured using ASTM D7426-08 (2008).

Plasticizer

If the glass transition temperatures of the color coating and/or the constituents of the film forming and pretreatment compositions are too high for the desired use yet the other properties thereof are appropriate, such as but not limited to color and remanence, one or more plasticizers can be combined with the constituents of the film forming and pretreatment composition embodiments so as to lower the T_(g) of the constituents and provide the appropriate feel and visual properties to the color coating. The plasticizer can be incorporated directly into one or both of the film forming and pretreatment compositions or can be applied to the hair following formation on the keratin fibers of the color composition of the combined film forming and pretreatment compositions but substantially curing the color composition to form the color coating on the keratin fibers. The plasticizer can be chosen from the plasticizers typically used in the field of application. Appropriate selection includes choice of a plasticizer that does not interfere with or compete with the in situ in situ acid-CDI addition and the alkoxysilyl condensation.

The plasticizer or plasticizers can have a molecular mass of less than or equal to 5,000 g/mol, such as less than or equal to 2,000 g/mol, for example less than or equal to 1,000 g/mol, such as less than or equal to 900 g/mol. In at least one embodiment, the plasticizer, for example, has a molecular mass of greater than or equal to 40 g/mol.

Thus, the film forming and pretreatment compositions can also comprise at least one plasticizer. For example, non-limiting mention can be made, alone or as a mixture, of common plasticizers such as: glycols and derivatives thereof, silicones, silicone polyethers, polyesterpolyols; adipic acid esters (such as diisodecyladipate), trimellitic acid esters, sebacic acid esters, azalaeic acid esters; nonlimiting examples of glycol derivatives are diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether or diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, or ethylene glycol hexyl ether; polyethylene glycols, polypropylene glycols, polyethylene glycol-polypropylene glycol copolymers, and mixtures thereof, such as high molecular weight polypropylene glycols, for example having a molecular mass ranging from 500 to 15,000, for instance glycol esters; propylene glycol derivatives such as propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, diethylene glycol methyl ether, and dipropylene glycol butyl ether. Such compounds are sold by Dow Chemical under the names DOWANOL PPH and DOWANOL DPnB; acid esters, for example esters of carboxylic acids, such as triacids, citrates, phthalates, adipates, carbonates, tartrates, phosphates, and sebacates; esters derived from the reaction of a monocarboxylic acid of formula R₁₁COOH with a diol of formula HOR₁₂OH in which Ru and R¹², which can be identical or different, are chosen from a linear, branched or cyclic, saturated, or unsaturated hydrocarbon-based chain containing, for example, from 3 to 15 carbon atoms for example the monoesters resulting from the reaction of isobutyric acid and octanediol such as 2,2,4-trimethyl-1,3-pentanediol, such as the product sold under the reference TEXANOL ESTER ALCOHOL by the company Eastman Chemical; oxyethylenated derivatives, such as oxyethylenated oils, such as plant oils, such as castor oil; mixtures thereof.

Among the esters of tricarboxylic acids mention can be made of the esters of triacids wherein the triacid corresponds to formula

wherein R is a group —H, —OH or —OCOR′ wherein R′ is an alkyl group containing from 1 to 6 carbon atoms. For example, R can be a group —OCOCH₃. The esterifying alcohol for such tricarboxylic acids may be those described above for the monocarboxylic acid esters.

The plasticizer can be present in either or both of the film forming and pretreatment compositions in an amount from about 0.01% to 20%.

Pigment

The film forming and pretreatment composition embodiments of the present invention make it possible to obtain colored coatings, without substantially altering the keratin fibers. As used herein, the terms “pigment(s) and color body(ies)” are synonyms and generally refer to any particle colorant or amorphous insoluble color material/body having or containing pigment material that gives keratin fibers color including black and white, such as titanium dioxide that gives only white color to keratin fibers. The pigments are substantially water-insoluble. The pigments, to distinguish from dyes presented in molecular from, are also referred to as pigment microparticles or pigment particles. The terms pigment microparticles and pigment particles are synonymous and are used herein interchangeably. The pigments can be organic, inorganic, or a combination of both. The pigments may be in pure form or coated, for example with a polymer or a dispersant.

Selections, multiple kinds and varying forms of the pigment microparticles as described in the following passages can be incorporated in any of the first, second and third components of the multicomponent composition, or can be incorporated in any two of these components or in all three. Preferably, pigment microparticles can be incorporated in either or both of the first and second components. More preferably, pigment particles can be incorporated in the first component.

The at least one pigment that can be used can be chosen from the organic and/or mineral pigments known in the art, such as those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry. The pigments comprised in the microparticles comprising at least one pigment will not substantially diffuse or dissolve into keratin fibers. Instead, the pigment comprised in the microparticles comprising at least one pigment will substantially remain separate from but attached to the keratin fibers.

The at least one pigment can be in the form of powder or of pigmentary paste. It can be coated or uncoated. The at least one pigment can be chosen, for example, from mineral pigments, organic pigments, elemental metal and their oxides, and other metal modifications, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.

Pigment Shape

The pigment microparticles can have any suitable shape, including substantially spherical. But the pigment microparticles can also be oval, elliptical, tubular, irregular, etc., or even combinations of various shapes. In addition, the pigment microparticles can have two dimensions, length and width/diameter, of similar magnitude. In addition, the pigment microparticles can be micro platelets, i.e. having a thickness that is substantially smaller than the planar dimension. For example, five, ten or even 20 times smaller in thickness than in the planer dimension. In one embodiment with any of the reactive components of the instant invention, the pigments may be surface treated, surface coated or encapsulated.

Pigment Size

The pigments can be present in the composition in undissolved form. Depending on the shape, the pigments can have a D50[vol] particle diameter of from 0.001 micron to 1 micron.

According to an embodiment, the particle size distribution, either relative to the number or volume of the particles, of the pigment microparticles can be at least bi-modal. A bi-modal particle size distribution has two distinct peaks which are spaced relative from, while tri-modal particle size distribution has three distinct peaks. The term “peak” means a local maximum of the distribution curve. The “distance” between two peaks, expressed relative to the particle size, can be at least 0.05 micron, preferably at least 0.1 micron, such as at least 0.2 micron. Providing an at least bi-modal particle size distribution allows to tailor the optical appearance of the colored hair. For example, the scattering properties varies with the particle size so that particles of different size scatter the light into different directions.

Pigments made from metal and metal like materials which can conduct electricity, and which can absorb light and re-emit the light out of the metal to give the appearance of strong reflectance. While not wishing to be bound by any specific theory, it is believed that the absorbed light will induce alternating electric currents on the metal surface, and that this currents immediately re-emit light out of the metal. Such pigment microparticles can be platelets, e.g., having a thickness that is substantially smaller than the planar dimension. For example, about five, about 10 or even about 400 times smaller in thickness than in the planer. Such platelets can have a planar dimension less than about 30 nm, but with a thickness less than about 10 micron wide. This includes a ratio of 10000 to 30, or 333. Platelets larger in size, such as 50 microns are even available in this thickness of 10 microns, and so the ratios can even go up to 2000.

The pigment microparticles can be a composite formed by two different types of pigment microparticles. Examples include a composite of a 2-dimensional microparticle and at least one micro spherical particle (microsphere), a composite of different micro spherical particles, and a composite of different 2-dimensional particles. Composite particles formed by 2-dimensional microparticles to which micro spherical particles adhere provide an attractive alternative to a pure mixture of 2-dimensional microparticles and micro spherical particles. For example, a metallic 2-dimensional microparticle can carry one or more micro spherical particle such as one or more organic micro spherical particle. The micro spherical particles attached or bonded to the 2-dimensional microparticle can be formed of the same pigment material or can be formed of different pigment material. Composite microparticles formed of 2-dimensional microparticles and micro spherical particles can provide multiple functionality in one particle such as (metallic) reflectance and dielectric scattering, reflectance and absorption.

The pigment microparticles can be both light scattering and absorbing for wavelengths of visible light. While not wishing to bound by any specific theory, it is believed that such pigments can provide both some visual effect of lightening the hair. Such pigment microparticles can have a D50[num] value between about 50 nm and about 750 nm, between about 100 nm and about 500 nm or between about 150 nm and about 400 nm. Such materials have a refractive index above about 1.5, above about 1.7 or above about 2.0.

According to an embodiment, different pigment microparticles are combined to provide reflective, transmitting and refractive properties of the hair colored with the color composition described herein. A microparticle combination can be a material composite using at least two different pigment materials to form the pigment microparticles. In addition to, or alternating to, the microparticle combination, a mixture of separate pigment microparticles of different type can be used to bring about the desired reflective, transmitting and refractive properties.

The composite pigments, combination of pigments, and mixtures of pigment microparticles eliminate, or at least significantly reduce, hair penetration and scattering by light and thus eliminate the perception of pigment of natural hair color change.

Pigment Concentration

The film forming composition for coloring hair fibers according to the present disclosure comprises microparticles comprising at least one pigment. The film forming composition comprises from about 0.01% to about 40%, about 0.05% to about 35%, about 0.1 to about 25%, or about 0.15% and about 20% pigment(s), by weight of the film forming composition.

Pigment Material

The material of the pigment microparticles can be inorganic or organic. Inorganic-organic mixed pigments are also possible.

According to an embodiment, inorganic pigment(s) may be used. The advantage of inorganic pigment(s) is their excellent resistance to light, weather, and temperature.

The inorganic pigment(s) can be of natural origin, and are, for example, derived from material selected from the group consisting of chalk, ochre, umber, green earth, burnt sienna, and graphite. The pigment(s) can preferably be white pigments, such as, for example, titanium dioxide or zinc oxide. The pigment(s) can also be colored pigments, such as, for example, ultramarine or iron oxide red, luster pigments, metal effect pigments, pearlescent pigments, and fluorescent or phosphorescent pigments. The pigment(s) can be selected from the group consisting of metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates, alloys, and the metals themselves. The pigment(s) can be selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), Prussian blue (ferric ferrocyanide, CI 77510), carmine (cochineal), zinc sulfide, barium sulfate, zinc oxide, derivatized titanium dioxide, derivatized zinc sulfide, derivatized zinc oxide, and mixtures thereof. The pigment(s) can be selected from the group consisting of iron oxide, titanium dioxide, mica, borosilicate, and combinations thereof. The pigment(s) can comprise an iron oxide (Fe₂O₃) pigment. The pigment(s) can comprise a combination of mica and titanium dioxide.

The pigment(s) can be pearlescent and colored pigment(s), and can preferably be based on mica which are coated with a metal oxide or a metal oxychloride, such as titanium dioxide or bismuth oxychloride, and optionally further color-imparting substances, such as iron oxides, Prussian blue, ultramarine, and carmine. The color exhibited by a pigment can be adjusted by varying the layer thickness. Such pigments are sold, for example, under the trade names Rona®, Colorona®, Dichrona®, RonaFlair®, Ronastar®, Xirona® and Timiron® all of which are available from Merck, Darmstadt, Germany. For example, Xirona® is a brand for color travel pigments that display color shifting effects depending on the viewing angle and are based on either natural mica, SiO₂ or calcium aluminum borosilicate flakes, coated with varying layers of TiO₂. Pigment(s) from the line KTZ® from Kobo Products, Inc., 3474 So. Clinton Ave., So. Plainfield, USA, are also useful herein, in particular the Surface Treatable KTZ® Pearlescent Pigments from Kobo. Particularly useful are KTZ® FINE WHITE (mica and TiO₂) having a D50 particle diameter of 5 to 25 micron and also KTZ® CELESTIAL LUSTER (mica and TiO₂, 10 to 60 micron) as well as KTZ® CLASSIC WHITE (mica and TiO₂, 10 to 60 micron). Also useful are SynCrystal Sapphire from Eckart Effect Pigments, which is a blue powder comprising platelets of synthetic fluorphlogopite coated with titanium dioxide, ferric ferrocyanide and small amounts of tin oxide. Also useful is SYNCRYSTAL Almond also from Eckart, which is a beige powder with a copper reflection color and is composed of platelets of synthetic fluorphlogopite and coated with titanium dioxide and iron oxides. Also useful is Duocrome® RV 524C from BASF, which provides a two color look via a lustrous red powder with a violet reflection powder due to its composition of mica, titanium dioxide and carmine. The colored pigment(s) can be lightly bright colored pigment(s) and can particularly be white color variations.

The pigment(s) can be organic pigments. The at least one pigment can be an organic pigment. As used herein, the term “organic pigment” means any pigment that satisfies the definition in Ullmann's encyclopedia in the chapter on organic pigments. For instance, the at least one organic pigment can be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, 7-Bis(1,3-dichloropropan-2-yl)benzo[lmn][3,8]phenanthrolin-1,3,6,8(2H,7H)-tetraon, copper hexadecachlorophthalocyanine, 2-[(2-Methoxy-4-nitrophenyl)azo]-N-(2-methoxyphenyl)-3-oxobutyramide, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, dimethylquinacridone and quinophthalone compounds, Azo-dyes, Nonionic azo dyes, Anionic Azo dyes, Cationic azo dyes, Complex forming azo dye, aza annulene dyes, aza analogue of diarylmethane dyes, aza annulene dyes, Nitro-dyes and their pigments, Carbonyl dyes and their pigments (for example, Anthrachinon dyes, indigo), Sulfur dyes, Florescence dyes, Anthracene or Insoluble alkali or earth metal acid dyes. Or the pigment can be at least one of uncolored and UV absorbing.

The organic pigment(s) can be selected from the group consisting of natural pigments sepia, gamboge, bone charcoal, Cassel brown, indigo, chlorophyll and other plant pigments. The synthetic organic pigments can be selected from the group consisting of azo pigments, anthraquinoids, indigoids, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue, diketopyrrolopyrrole pigments, and combinations thereof. A particularly preferred pigment is 7-Bis(1,3-dichloropropan-2-yl)benzo[lmn][3,8]phenanthrolin-1,3,6,8(2H,7H)-tetraon.

The pigment(s) used in the color composition can include at least two different pigments selected from the above pigment group, or can include at least three different pigments selected from the above pigment group. According to an embodiment, the pigment(s) used in the color composition can include at least one yellow pigment selected from the yellow pigment group consisting of: a Pigment Yellow 83 (CI 21108), CAS #5567-15-7, Pigment Yellow 155 (C.I. 200310), (CAS: 68516-73-4), Pigment Yellow 180 (C.I. 21290), (CAS: 77804-81-0).

In addition to the at least one yellow pigment, or alternatively, the pigments(s) used in the color composition can include at least one red pigment selected from the red pigment group consisting of: Pigment Red 5 (CI 12490), (CAS #6410-41-9), Pigment Red 112 (CI 12370), (CAS #6535-46-2), Pigment Red 122 (CI 73915), (CAS #980-26-7).

In addition to the at least one yellow pigment and/or the at least one red pigment, or alternatively, the pigments(s) used in the color composition can include at least one green pigment selected from the green pigment group consisting of: Pigment Green 36, (C.I. 74265), (CAS: 14302-13-7).

In addition to the at least one yellow pigment and/or the at least one red pigment and or the at least one green pigment, or alternatively, the pigments(s) used in the color composition can include at least one blue pigment selected from the blue pigment group consisting of: Pigment Blue 16, (CAS: 424827-05-4), Pigment Blue 60 (C.I. 69800), (CAS: 81-77-6), Pigment Blue 66, (C.I. 73000), (CAS: 482-89-3)

In addition to the at least one yellow pigment and/or the at least one red pigment and/or the at least one green pigment, and/or the at least one blue pigment or alternatively, the pigments(s) used in the color composition can include at least one black pigment selected from the black pigment group consisting of: Pigment Black 6 (C.I. 77266), (CAS 1333-86-4), Pigment Black 7 (C.I. 77266), (CAS 1333-86-4). An additional combination can include aluminium flake with a red, blue, green, yellow or any combination thereof.

The pigment(s) can optionally have a surface zeta potential of ≥±15 Mv, preferably ≥±20 Mv, more preferably ≥±25 Mv. The surface zeta potential can be measured with a zetasizer, for example, a Zetasizer 3000 HS. Surface zeta potential measurements are conducted, for example, according to ISO 13099.

For example, the white or colored organic pigments can be chosen from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, 52erivatized52ne blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100, and 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21090, 21100, 21108, 47000, 47005 and 77492.

The green pigments codified in the Color Index under the references CI 61565, 61570, 74265, and 74260, the orange pigments codified in the Color Index under the references CI 11725,12075, 15510, 45370, and 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15585, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 45430, 58000, 73360, 73915, 75470, and 77491 and the pigments obtained by oxidative polymerization of indole or phenolic derivatives.

Non-limiting examples that can also be mentioned include pigmentary pastes of organic pigments, such as the products sold by the company Hoechst under the names: JAUNE COSMENYL IOG: Pigment Yellow 3 (CI 11710); JAUNE COSMENYL G: Pigment Yellow 1 (CI 11680); ORANGE COSMENYL GR: Pigment Orange 43 (CI 71105); ROUGE COSMENYL R: Pigment Red 4 (CI 12085); CARMINE COSMENYL FB: Pigment Red 5 (CI 12490); VIOLET COSMENYL RL: Pigment Violet 23 (CI 51319); BLEU COSMENYL A2R: Pigment Blue 15.1 (CI 74160); VERT COSMENYL GG: Pigment Green 7 (CI 74260); and NOIR COSMENYL R: Pigment Black 7 (CI 77266).

The at least one pigment in accordance with the present disclosure can also be in the form of at least one composite pigment as described in European Patent Publication No. EP 1 184 426 A2. These composite pigments can be, for example, compounds of particles comprising a mineral core, at least one binder for ensuring the binding of the organic pigments to the core, and at least one organic pigment at least partially covering the core.

The at least one pigment in accordance with the present disclosure can be in the form of small undissolved microparticles, which do not diffuse into the hair color, but deposit on the outer wall of the keratin fiber. Suitable color pigments can be of organic and/or inorganic origin. But the pigments can also be inorganic color pigments, given the excellent light, weather and/or temperature resistance thereof.

Inorganic pigments, whether natural or synthetic in origin, include those produced from chalk, red ocher, umbra, green earth, burnt sienna or graphite, for example. Furthermore, it is possible to use black pigments, such as iron oxide black, color pigments such as ultramarine or iron oxide red, and fluorescent or phosphorescent pigments as inorganic color pigments.

Colored metal oxides, metal hydroxides and metal oxide hydrates, mixed phase pigments, sulfurous silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, metal chromates and/or metal molybdates are particularly suitable. In particular, preferred color pigments are black iron oxide (Cl 77499), yellow iron oxide (Cl 77492), red and brown iron oxide (Cl 77491), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfosilicates, Cl 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510) and/or carmine (cochineal).

The at least one pigment can also be colored pearlescent pigments. These are usually mica-based and can be coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (Cl 77491, CI 77499), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and/or iron blue (ferric ferrocyanide, CI 77510).

Mica forms part of the phyllosilicates, including muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. To produce the pearlescent pigments in combination with metal oxides, the mica, primarily muscovite or phlogopite, is coated with a metal oxide.

The at least one pigment can also be at least one mica-based colored pigment, which is coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and/or brown iron oxide (Cl 77491, CI 77499), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and/or iron blue (ferric ferrocyanide, CI 77510).

The at least one pigment can also be color pigments commercially available, for example, under the trade names Rona®, Colorona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors, and Sunshine® from Sunstar.

The at least one pigment can also be color pigments bearing the trade name Colorona® are, for example: Colorona Copper, Merck, MICA, Cl 77491 (IRON OXIDES); Colorona Passion Orange, Merck, Mica, Cl 77491 (Iron Oxides), Alumina; Colorona Patina Silver, Merck, MICA, Cl 77499 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE); Colorona RY, Merck, Cl 77891 (TITANIUM DIOXIDE), MICA, Cl 75470 (CARMINE); Colorona Oriental Beige, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES); Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE; Colorona Chameleon, Merck, Cl 77491 (IRON OXIDES), MICA; Colorona Aborigine Amber, Merck, MICA, Cl 77499 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE); Colorona Blackstar Blue, Merck, Cl 77499 (IRON OXIDES), MICA; Colorona Patagonian Purple, Merck, MICA, Cl 77491 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE), Cl 77510 (FERRIC FERROCYANIDE); Colorona Red Brown, Merck, MICA, Cl 77491 (IRON OXIDES), Cl 77891 (TITANIUM DIOXIDE); Colorona Russet, Merck, Cl 77491 (TITANIUM DIOXIDE), MICA, Cl 77891 (IRON OXIDES); Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), D&C RED NO. 30 (Cl 73360); Colorona Majestic Green, Merck, Cl 77891 (TITANIUM DIOXIDE), MICA, Cl 77288 (CHROMIUM OXIDE GREENS); Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), FERRIC FERROCYANIDE (Cl 77510); Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON); Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491); Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES); Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES); Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES); Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES); Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES); Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES); Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide; Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891, Cl 77491 (EU); Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides); Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES); color pigments bearing the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient Cl 77491 (Iron Oxides), Silica; Unipure Black LC 989 EM, Sensient, Cl 77499 (Iron Oxides), Silica; Unipure Yellow LC 182 EM, Sensient, Cl 77492 (Iron Oxides), Silica.

Among the dyes, non-limiting mention can be made of cochineal carmine. Non-limiting mention can also be made of the dyes known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 0 (CI 77 002), D&C Green 3 (CI 42 053), and D&C Blue 1 (CI 42 090). A non-limiting example of a lake that can be mentioned is the product known under the following name: D&C Red 7 (CI 15 850:1).

Color Gamut for Pigment Blends

CIE L*a*b* (CIELAB) is a color space specified by the International Commission on Illumination. It describes all the colors visible to the human eye and serves as a device-independent model to be used as a reference.

The three coordinates of CIELAB represent the lightness of the color (L*=0 yields black and L*=100 indicates diffuse white; specular white may be higher), its position between red/magenta and green (a*, negative values indicate green while positive values indicate magenta) and its position between yellow and blue (b*, negative values indicate blue and positive values indicate yellow).

Since the L*a*b* model is a three-dimensional model, it can be represented properly only in a three-dimensional space. Two-dimensional depictions include chromaticity diagrams: sections of the color solid with a fixed lightness.

Because the red-green and yellow-blue opponent channels are computed as differences of lightness transformations of (putative) cone responses, CIELAB is a chromatic value color space.

In the present invention, the color gamut is determined by preparing samples of the film forming composition without pigment and the adding each pigment to be tested to individual samples of the film forming composition. Samples with pigment are prepared and applied to tress substrates. The samples are cured and then tested for coloration so that the resulting CIELAB lightness or L* value of the colored hair is 60±2. The level of pigment needed will depend on the pigment being tested. For example, hair tresses (Kerling, Natural White special quality) can be prepared as described using samples of a film forming composition applied alone as described in the present invention. A Minolta spectrophotometer CM-2600d can be used to measure the color of the cured and dried hair tresses, five points on both the front and back sides, and the values averaged. The D65 L*a*b values can be calculated. When at least three pigments have each been measured such that their resulting colors reside within the target L* values of 60±2 the color gamut can be calculated. First the lengths of each side of the resulting triangle of each combination of three pigments in the a*b plane are computed using the following expressions. To calculate the distance between pigments 1 and pigment 2 the following equation is used:

Side Length SL₁₂=((a _(pigment 1) −a _(pigment 2))²+(b _(pigment 1) −b _(pigment 2))²)²)^(0.5).

This is computed for each pair of pigments. Then for a series of three pigments.

The resulting color gamut is calculated using the expression:

Color Gamut=(S(S−SL₁₂)(S−SL₁₃)(S−SL₂₃))^(0.5)

wherein SL₁₂, SL₁₃, and SL₂₃ are the three lengths of the sides of the triangle within the a*b plane, and S=(SL₁₂+SL₁₃+SL₂₃)/2. Where more than three pigments are used, this calculation can be performed for each combination of the three pigment from the more than three pigments used, and the largest Color Gamut is selected.

The color coating embodiments of the present invention can also have a color gamut of greater than 250, greater than 500, greater than 750, greater than 800, greater than 900, greater than 1100 or even greater than 1250.

Experiments Performed for Color Gamut

Using the above expression, for each combination of three pigments possible from Color Gamut Tables 1, as illustrated below, the color gamut at a nominal L value of 60 was calculated.

TABLE 1 Color Gamut wt % Pigment Name Supplier level L a b Blue 15 PV Fast Blue BG-NIP Clariant 0.155 59.3 −18.7 −2.1 Blue 16 Phthalocyanine Carbosynth 0.280 59.4 −17.3 1.5 Blue 66 Indigo 229296 Aldrich 0.105 60.0 −3.1 6.8 Blue 60 Paliogen Blau L 6482 BASF 0.260 60.7 −3.9 5.9 Black 7 Midnight Black Geotech 0.045 59.8 0.0 12.3 Green 36 Heliogen Green K 9362 BASF 0.509 60.1 −32.8 20.2 Red 112 Permanent Red FGR 250 Clariant 0.150 60.1 29.8 18.8 Red 122 Hostaperm Pink E02-EDW Clariant 0.140 59.5 24.9 6.1 VP4034 Violet 19 Ink Jet Magenta E5B 02 Clariant 0.200 60.6 28.1 10.1 M250 Red 5 Permanent Carmine FB01 Clariant 0.140 59.7 30.1 14.4 Yellow 155 Ink Jet Yellow 4GC Clariant 16.92 61.8 9.6 74.4 Yellow 83 Novoperm Yellow HR 70 Clariant 1.059 60.0 12.5 61.8 Yellow 180 Toner Yellow HG Clariant 9.16 61.4 11.2 72.8

These were formulated within an example formulation described later using an appropriate level of first, second and third compositions.

A few examples are exemplified of combinations of pigments and their resulting color gamut. One skilled in the art would be able to perform this for all of the possible permutations of pigments that are assessed according the description above.

FIGS. 1 to 6 show plots of color gamut triangles created for a series of three pigment selections. FIG. 1 shows that a combination of Pigment Green 36, Pigment Yellow 83 and Pigment Red 122 a large triangle is plotted in the a*b* color plane with an area of 1520. FIG. 2 shows that the combination of Pigment Green 36, Pigment Yellow 83 and Pigment Blue 60 gives a smaller triangle win an area of 925. FIG. 3 shows the combination of Pigment Black 7, Pigment Yellow 83 and Pigment Red 122 gives a smaller triangle win an area of 655. FIG. 4 shows the combination of Pigment Black 7, Pigment Blue 60 and Pigment Red 122 gives a smaller triangle win an area of 92.

A second series of example are made for how to assess more than three pigments and their resulting color gamut. When plotted a series of triangles can be plotted as shown and for each the areas is assessed. For such a composition the color gamut is defined as the largest of the triangles formed.

FIG. 5 shows a combination of Pigment Green 36, Pigment Yellow 83, Pigment Blue 60 and Pigment Red 122 a series of triangles are plotted with areas of 803, 925, 209 and 1520. The color gamut of this pigment composition is 1520. [Alterative calculation of total area would yield, 1728] FIG. 6 shows a combination of Pigment Black 7, Pigment Yellow 83, Pigment Blue 60 and Pigment Red 122 a series of triangles are plotted with areas of 803, 57, 92 and 655. The color gamut of the pigment composition is 803 [alternative approach would be the same]

In an embodiment, a color composition (e.g., a set of a film forming composition and a pretreatment composition applied sequentially, simultaneously or in premixture to keratin fibers) can be applied to the hair in a sequential manner. For example it may be that this first set is applied to the hair which contains pigment microparticles that substantially scatter and/or reflect light such that it produces the visual effect of making the hair look lighter in color, after which a second set can be applied which contains pigment microparticles that substantially absorbs light and provides color to the hair and wherein the combination of the sequential addition of the first and second sets of color compositions provides the final hair color. For example, a first color composition may comprise metallic flakes and the second color composition may contain organic pigment microparticles. It may also be that more than a first and a second color composition are applied to the hair to achieve the desired color result, that three or more color compositions are applied.

The pH

The film forming and pretreatment composition embodiments in accordance with the present invention may have a pH adjustment attendant with their application to keratin fibers so that the pH upon application may range from about 4 to about 10, preferably about 5 to about 9. The pH is preferably dynamically managed to control the rate of reaction of the reactive constituents of the film forming and pretreatment compositions. Maintaining a slightly basic pH during the mixing and preapplication stages involving these compositions controls the acid-CDI addition and alkoxysilyl condensation under certain circumstances. The addition and condensation may be initiated by reversion of an acidic pH to an appropriate state for reaction.

Dispersants

It will be apparent to one skilled in the art that careful and selective choice of dispersant can help to maximize performance in terms of maximizing the amount of color produced from an immobilized film, maximizing the remanence or wash fastness, and enabling removal of the color.

The electrostatic, ionic and functional character of the dispersant is chosen to be compatible with and to not interfere with the reactive constituents of the film forming and pretreatment compositions. More preferably, the dispersant is chosen to be compatible with and miscible with the other components of the composition or compositions with and without medium.

The principle of choosing chemically similar dispersant with the binder polymer of the film forming composition can be followed to ensure maximum compatibility.

As well as compatibility as noted above, the other criterion in selecting dispersant(s) is their ability to enable pigment to be dispersed down to the primary particle size, preferably with the minimum amount of input mechanical energy. It will be recognized by someone skilled in the art that the concentration of dispersing agent is also a factor. In general, it is usually required that there is a minimum amount for dispersing activity and that below this, the composition is either not fully dispersed or the dispersant acts as a flocculant.

These two considerations together are used to define preferred materials and their respective concentrations.

It may also be the case, depending on the type of binder polymer used, that the binder itself is also a dispersant. In such cases it is possible that no further dispersing additive may be needed.

Combination of the dispersed pigment mixture with the film forming composition can be made in any manner. This order of combination of the dispersed pigment mixture with the film forming composition delivers the dispersed pigment mixture with the film forming composition layer and on top of the pretreatment layer. While the layers intermix to a slight to moderate to essentially full extent, at least a portion of the dispersed pigment mixture resides over the pretreatment layer. This arrangement of the coating at least in part enables removal of the coating when the “off” techniques described below are practiced.

Dispersants, Kinds, Properties and Chemistry

Dispersants are amphiphilic or amphiphathic meaning that they are chemical compounds possessing both hydrophilic (water-loving, polar) and lipophilic (fat-loving) properties. Dispersants are surface-active polymers that allow the homogeneous distribution and stabilization of solids, e.g. pigments in a liquid medium, by lowering the interfacial tension between the two components. As a result, agglomerates are broken up into primary particles and protected by a protecting dispersant envelope of a re-agglomeration.

The dispersants can be subdivided on the basis of the stabilization mechanism in

1. dispersants for electrostatic stabilization

a. Anionic dispersing additives

-   -   i. Polyacrylates     -   ii. Polyphosphates

b. Neutral dispersing additives, e.g, nonionic surfactants

c. Cationic dispersing additives, e.g., quaternary ammonium organic and/or silicone polymers

2. Dispersants for steric stabilization

Electrostatic Stabilization

The pigment surface is occupied by an additive carrying an ionic charge. All pigment particles are charged the same. The mutual repulsion by the charge is greater than the attractions of the pigment particles. The electrostatic stabilization has its relevance mostly in water-based paint compositions.

Polyanionic dispersing additives: polycarboxylates (mostly salts of polyacrylic acids), polyphosphates divided into linear polyphosphates and cyclic metaphosphates, polyacrylates

salts of polyacrylic acid, as cations, sodium and ammonium are preferred, these polyacrylates are water-soluble, technical products have molecular weights in the range of 2000 to 20,000 g/mol, optimum is about 8000 g/mol

Sodium and ammonium salts of the homo- or copolymers of acrylic acid, methacrylic acid or maleic acid

Steric Stabilization

The attractive forces between the pigment particles are effective only over relatively small distances of the particles from each other. The approach of two particles to each other can be prevented by molecules that are firmly anchored to the pigment surface and carry groups that extend from the surface and may reduce the potential for the pigments to contact one another. By sufficiently long chain lengths, agglomeration can be prevented. Also, the substances added to avoid agglomeration and other undesirable pigment particle interactions preferably are chosen to minimize or avoid interaction with the reactive polymers of the color composition.

Incorporation of Pigment in Dispersant

The pigments described herein can be chosen and/or modified to be similar enough such that a single dispersant can be used. In other instances, where the pigments are different, but compatible, two or more different dispersants can be used. Because of the extreme small size of the pigment microparticles and their affinity, combination of the pigment microparticles and dispersant to form a substantially homogeneous dispersion that can subsequently be modified and/or diluted as desired is to be accomplished before combination with any or all of the first, second and third components of the multicomponent composition and preferably with only the first and/or second components.

The pigment microparticles can be dispersed and stabilized in the medium by one or more dispersants the properties and kinds of which are described above. The dispersant can either be added to the medium, or to a precursor medium or can form a coating on the microparticles to facilitate dispersion. It is also possible to provide the microparticles with a coating of a dispersant material and additionally provide a further dispersant to the medium, or to a precursor medium, which is used to form the final medium.

The dispersant, either added to the medium or provided as coating, facilitates wetting of the microparticles, dispersing of the microparticles in the medium, and stabilizing of the microparticles in the medium.

The wetting includes replacing of materials, such as air, adsorbed on the surface of the pigment microparticles and inside of agglomerates of the microparticles by the medium. Typically, a complete wetting of the individual microparticles is desired to singularize the particles and to break off agglomerates formed by microparticles adhering to each other.

After wetting, the microparticles can be subjected to de-aggregate and de-agglomerate step, generally referred to as dispersing step. The dispersing step typically includes the impact of mechanical forces such as shear to singularize the microparticles. In addition to shearing to singularize, the microparticles can be broken into even smaller microparticles using, for example, roller mills, high speed mixers, and bead mills. Usual practice involves substantially homogeneous dispersion of the pigments in dispersant through the use of high shear mixing; for example, through use to the appropriate ball mill, ultra high-pressure homogenizer or other composition known by those skilled in the art of pigment dispersion.

During wetting and dispersing, the exposed total surface area of the microparticles increases which is wetted by the dispersant. The amount of the dispersant may be gradually increased during dispersing to account for the increased surface area.

The dispersant also functions as de-flocculation agent keeping the dispersed microparticles in a dispersed state and prevent that they flocculate to form loose aggregates. This stabilization is also needed for long term storage purposes. Different type of stabilization such as electrostatic stabilization and steric stabilization are possible, and the type of dispersant is selected in view of the medium and the material of the microparticles.

The dispersant may be added to a dry powder of the pigment particles when the particles are milled to a desired size. During milling, or any other suitable technique to singularize the pigment particles or to break them into smaller part, the dispersant comes in contact with and adheres to the surface of the microparticles. Freshly generated microparticle surface during milling will be coated by the dispersant so that, after milling, the microparticles with a coating formed by the dispersant are provided.

The coating with the dispersant can also be carried out in a liquid carrier medium to which the dispersant is added. The microparticles can also be milled in the liquid carrier.

Optionally, the pigment microparticles may be coated with small molecules from a pretreatment composition. A portion of the pretreatment composition may be combined with the pre-milled pigment particles according to the procedures described above for wetting and dispersing the microparticles with dispersant. Following the wetting and dispersing procedures, the processed microparticles may be separated from excess pretreatment composition to produce microparticles coated with small molecules. It is believed that during this procedure, the coating of small molecules will begin to condense so that the coating will be at least a partially condensed net of silicone coating the individual microparticles. The coated microparticles may then be wetted and dispersed in dispersant as described above for the wetting and dispersing procedures.

Additive Components

Additive components for the film forming composition include suspending agents, leveling agents and viscosity control agents. The suspending agents help maintain the pigment particles in dispersed condition and minimize or negate their agglomeration. Suspending agents include fatty acid esters of polyols such as polyethylene glycol and polypropylene glycol. These are similar to plasticizers and function in similar fashion to allow pigment particles to “slip” by each other without retarding or binding interaction. They act as grease in this fashion. Additionally, suspending agents in part participate in promoting the stable dispersion of the pigment particles and avoid settling. The binder and linker of the film forming composition also participate through their solubilization or interaction with the pigment particles and with the medium. The suspending agents provide another factor for maintaining the stable dispersion. They not only provide the “grease” to facilitate Brownian movement but also in part stabilize through interaction as emulsifiers of the pigment particles in the medium. Optional components also are to be chosen so that they do not interfere or only minimally interfere with the reactive polymer coupling reaction.

Embodiments of the film forming composition in accordance with the present invention can also optionally contain at least one adjuvant, chosen, for example, from reducing agents, fatty substances, softeners, antifoams, moisturizers, UV-screening agents, mineral colloids, peptizers, solubilizers, fragrances, anionic, cationic, nonionic, or amphoteric surfactants, proteins, vitamins, propellants, oxyethylenated or non-oxyethylenated waxes, paraffins, C₁₀-C₃₀ fatty acids such as stearic acid or lauric acid, and C₁₀-C₃₀ fatty amides such as lauric diethanolamide.

Embodiments of the film forming composition in accordance with the present invention can further optionally contain one or more additives, including, but not limited to, antioxidants (e.g., phenolics, secondary amines, phosphites, thioesters, and combinations thereof), non-reactive diluents (e.g., ethylene glycol, di(ethylene glycol), tetra(ethylene glycol), glycerol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, triethylene glycol monomethyl ether, 2-ethoxyethanol, solketal, benzonitrile, hexamethylphosphoramide, 2-N-methylpyrrolidinone and N,N-dimethylformamide); dyes, fillers (e.g., silica; carbon black; clay; titanium dioxide; silicates of aluminum, magnesium, calcium, sodium, potassium and mixtures thereof; carbonates of calcium, magnesium and mixtures thereof; oxides of silicon, calcium, zinc, iron, titanium, and aluminum; sulfates of calcium, barium, and lead; alumina trihydrate; magnesium hydroxide and mixtures thereof), plasticizers (e.g., petroleum oils such as ASTM D2226 aromatic oils; paraffinic and naphthenic oils; polyalkylbenzene oils; organic acid monoesters such as alkyl and alkoxyalkyl oleates and stearates; organic acid diesters such as dialkyl, dialkoxyalkyl, and alkyl aryl phthalates, terephthalates, sebacates, adipates, and glutarates; glycol diesters such as tri-, tetra-, and polyethylene glycol dialkanoates; trialkyl trimellitates; trialkyl, trialkoxyalkyl, alkyl diaryl, and triaryl phosphates; chlorinated paraffin oils; coumarone-indene resins; pine tars; vegetable oils such as castor, tall, rapeseed, and soybean oils and esters and epoxidized derivatives thereof; esters of dibasic acids (or their anhydrides) with monohydric alcohols such as o-phthalates, adipates and benzoates; and the like and combinations thereof), processing aids, ultraviolet stabilizers (e.g., a hindered amine, an o-hydroxy-phenylbenzotriazole, a 2-hydroxy-4-alkoxybenzophenone, a salicylate, a cyanoacrylate, a nickel chelate, a benzylidene malonate, oxalanilide, and combinations thereof), and combinations thereof.

An additional additive may be a tactile hair modification agent. These may include, but are not limited to, a softening and/or lubricating and/or anti-static and/or hair alignment and/or anti-frizz benefit and/or impact on the keratin fibers.

Additional additives include filler materials such as but not limited to no chromatic material with a particle size of from about 2 nm to about 500 nm; macromolecular strands or nanoparticles composed of polyolefin such as polyethylene, polypropylene, polybutene, and combinations thereof, clays and mineralite substances such as but not limited to smectites, kaolins, illites, chlorites, attapulgites and intercalated aluminosilicate materials and purified formed thereof and combinations thereof. Additional mineral microparticles may be composed of inorganic metal oxides selected from the group consisting of silica, titanium oxide, zirconium oxide, aluminum oxide, magnesium oxide, boehmite alumina, hydrotalcite. Still other filler material includes but is not limited to carbon nanotubes micrographitic material such as nanofiller of graphite oxide mixed polymer, microbucky balls, clathrates, and crown composites of organic and mineral complexes. Additionally, the filler may be combined, complexed, contain or incorporate a polymer containing one of the members of a complementary reactive pair relating to the first and second components of the reactive polymer composition.

Additives may also include but are not limited to UV filter and UV block substances such as but not limited to avobenzone, bemotrizinol octocrylene, benzophenone-4, ethylhexyl methoxycinnamate, PABA, padimate O, PBSA, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octyl salicylate, parsol Max, tinosorb S and A2B, Uvinul, amioxate, polyvinylidene fluoride and other similar conjugated organic compounds, radical scavengers, triplet formation inhibitors, metal compounds incorporating chromium, titanium, zinc, nickel, manganese, iron, niobium, silver, gold, aluminum, hafnium, tantalum such as the oxides and similar forms thereof wherein the metal compounds absorb or reflect UV light.

Topcoat

The topcoat composition is a post dressing composition that may be applied at a later time by the person whose hair has been dressed with the color coatings (hereinafter the user). The topcoat composition may also be applied to the user's hair by a salon professional who has previously dressed the user's hair with color coatings or who is in the process of dressing the user's hair. The topcoat typically contains a readily evaporable medium such as an aqueous alcohol mixture in combination with water repellant compounds, hair setting compounds that may be shampoo and/or water rinse removable, or hair setting compounds that may be slowly removable by cationic shampoo but not by water rinse or ordinary anionic shampoo typically applied as a home shampoo wash of hair.

Water repellant compounds for inclusion in the topcoat composition may include waxes, silicones, organofluoride compounds such as polytetrafluoroethylene. Preferred among such repellants is carnauba wax, beeswax, olefinic wax, paraffin. Polyurethanes, polyureas, polyesters, polysilicones and combinations thereof may also constitute constituents of the topcoat composition. Preferably, these polymers have significant numbers of non-reactive functional groups distributed throughout their polymer chains and as pendant groups so that hydrogen bonding, dipolar interaction and ionic interaction with the underlying films on the hair are produced. The presence of such polymers adds water repellency, shine and reasonable buoyancy character to the hair.

Hair setting compounds for inclusion in the topcoat composition may be readily removable with ordinary shampoo washing or may be long lasting in that multiple shampoo washings slowly will remove the hair setting compounds. The hair setting compounds enable retention of a particular set or coiffure under typical environmental conditions, such as rain, humidity and wind. Nevertheless, they may be removed by shampoo washing with commercially available shampoo formulations. The hair setting compounds useful for inclusion in the topcoat composition may be copolymers of an acidic vinyl monomer such as (meth) acrylic acid, a hydrophobic nonionic vinyl monomer such as alkyl (meth)acrylates, and first and second associative monomers such as polyoxyalkyenyl fumaric or similar unsaturated dicarboxylic acids. The compounds may be polyvinylpyrrolidones (PVP), copolymers of PVP and vinyl acetate (VA), acrylate and hydroxyalkyl acrylate copolymers, CARBOPOL (polyacrylic acid), CARBOPOL ETD polymer, xanthan gum, hydrophobically modified cellulose. Still other substances useful as hair setting compounds and as repellant compounds for topcoats are based upon (meth)acrylic copolymers of (meth)acrylic esters of C6 to C20 alkyl groups and (meth)acrylic esters of unsaturated alcohols and hydrophilic monomers such as (meth)acrylic acid. Copolymers of this formulation have unsaturation sites as films applied to the hair. A short UV irradiation of such copolymers as films enables cross linking and conveys wind, rain and shampoo resistance to the topcoat composition. Block copolymers of (meth)acrylic acid, crotonic acid, alkyl (meth)acrylates and minor percentages of olefinic monomers such as styrene provide the holding, low tackiness and high humidity resistance qualities to the topcoat while at the same time enabling readily removal with shampoo washing. Incorporation into the topcoat of a non-tacky pressure sensitive adhesive such as a copolymer of butyl acrylate and methacrylic acid with the percentage of methacrylic acid being minor on the order of 2 to 4 wt % also promotes hold and set. In some instances, a topcoat formulated with (meth)acrylate copolymers that are not readily removable by shampoo washing and display thermoplastic qualities at temperatures about at least 20° C. above human body temperature may be useful for reset of hair styles. This version of the topcoat may be warmed with a warm hair dryer and the hair reset to a new style. Cooling the reset hair provides the reset hair style as the thermoplastic polymer retains the shape provided by the reset.

The topcoat composition may contain the polymer compounds as microparticles dispersed in the medium or may be dissolved in solution with the medium. The topcoat optionally may contain pigment particles and dispersant as described above. The topcoat may be applied as a liquid composition using a brush, sponge or other similar applicator to coat individual hair strands. Alternatively, the topcoat composition may be incorporated into a spray pump container and applied as an aerosol to the hair. Applied as a spray the topcoat composition preferably is formulated to remain liquid on the hair for a sufficient time to enable gentle brushing to transfer the liquid throughout the hair strands and enable essentially all hair strands to be coated. When hair styling is part of the topcoat process, the hair may be set with mechanical devices or may be set with heat and mechanical manipulation as described above.

Post Care Composition

The post care composition typically may be applied by the user periodically to preserve the shine, color lastingness and character of the color coating of the hair. The post care composition incorporates ingredients that impart lubrication, feel modifiers, sacrificial semi-fluid films to the hair. Includes are non-ionic surfactants, cationic surfactants such as long chain quaternary ammonium compounds, amosilicone conditioners, fatty acid amide conditioners, fatty alcohol betaines and sultaines, non-penetrating surfactants with a molecular volume larger than about 450 cc per mol. The post care composition may be formulated in a medium such as an aqueous or aqueous alcoholic medium that is capable of volatilization over a short period of time, such as one to five minutes. The post care composition may be applied to keratin fibers as a spray or as a liquid. Also useful as a post care composition is a protective composition that may be applied as a mask to the skin and parts of the user that are not to be treated with the compositions described herein. The protective composition forms a thin film mask on the skin and is readily removable by peeling. Adhesion to the skin is minimal so that peeling does not injure the skin. Compounds in aqueous alcohol solution provide the mask film upon evaporation of the medium. Compounds such as polymers and copolymers of high Mw organic hydroxy acids such as lactic and glycolic acid provide useful peelable masks. The post case composition can be designed to specifically care for the coating on the surface, versus the surface itself. So for example in the context of a coating on the hair surface, rather than use a regular product that is designed to clean and condition the hair surface, the post care composition is tailored to look after and care for the coating upon the hair surface.

Solids Content

Embodiments of the film forming composition and pretreatment composition include solids and liquids. The solids comprise any substance or material of these compositions that in a form uncombined with any other material, solvent, liquid or substance is has a solid physical form at ambient conditions. Included at least are the polymers, small molecules and associated catalyst/promotor materials and the pigment microparticles of these compositions. The medium, in contrast is a liquid and functions as a solvent and/or a liquid in which solid particles are dispersed. The optional components as well as the plasticizer, dispersing agent, surface treatment agent, cross linking agent and other materials added to the medium, if any, are included in the solids content as long as they remain with the polymers, reaction materials and pigment microparticles following application and setting of the color composition and pretreatment composition as a coating on strands of human hair. This includes substances that ordinarily would be regarded as liquids because they would remain in the coating on strands of hair.

The solids content of the film forming composition and pretreatment composition may range from about 0.1 wt % to about 50 wt % relative to the total weight of the respective composition. A preferred solids content ranges from about 0.1 wt % to about 20 wt % and another preferred solids content ranges from about 0.2 wt % to about 12 wt % relative to the total weight of the composition. An especially preferred solids content range is about 0.3 wt % to about 11 wt % with contents of about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt % and about 8 wt % being more especially preferred.

Because the solids of the pretreatment composition is the small molecule, the foregoing solids content also indicates the concentration of small molecule in the pretreatment composition medium with the especially preferred solids content range being the preferred concentration of small molecule in the medium of the pretreatment composition.

The film forming composition includes the binder, the linker and the pigment or color bodies when the film forming composition is ready for application to keratin fibers. These three components are all solids and each constitutes a portion of the total solids content of the film forming composition ready for use. When the film forming composition is maintained separately as the binder and medium, as linker and medium and pigment and medium, the especially preferred solids content range given above is the preferred concentration of the binder in medium when stored in a separate container. The concentration of pigment in dispersant and medium in a separate container usually has a much higher concentration and in preparation for combination into the film forming composition, several of the different pigments are combined and diluted as described herein to form the coloration factor of the film forming composition. The linker is also in a low solids concentration range as described above when the linker is in storage. The linker is typically combined with the binder in medium just prior to application to keratin fibers.

The ratio of the concentration of film forming composition to pretreatment composition upon application to keratin fibers is adjusted to provide at least molar amounts to enable the small molecule and linker to inter-condense when the linker includes alkoxysilyl groups. Preferably, the molar amount of the small molecule is larger by from 2% to 20%, preferably 3% to 10%, more preferably from about 5% to about 10% relative to the molar amount of the linker. The concentrations and molar amounts designed to deliver concentrations of from 2 wt % to 4 wt % of the small molecule in the pretreatment composition and the linker in the film forming composition and preferably a molar excess of small molecule relative to the linker are calculated and measured into delivery containers so that application of a metered container of the pretreatment composition onto a portion of hair followed by application of a metered container of film forming composition onto the same portion of hair will deliver the desired results of small molecule and linker inter-condensation.

Testing the Flexibility of a Coating

With the color coating prepared on a releasable substrate and isolated as a standalone polymer film it can also be tested for optical density to check that the polymer film does not itself alter the hair appearance of the hair too significantly.

Further the polymer film preferably can be tested to reveal its glass transition point (Tg) as described above so that it is possible to prevent the colored coating from being damaged or cracked and to secure washing and friction remanence.

The color coating can have a surface energy between about 20 and about 50 Mn m⁻¹. The color coating binder/linker combination without pigments or color bodies preferably has high transmission, to ensure that it does not interfere with the optics of the hair color. The cured polymer film preferably has a refractive index between 1.4 and 1.6.

Ultimate elongation. The term ultimate elongation refers to the amount of elongation a given material can experience under a specific test method before failure occurs and the material breaks into more than one piece. It is the separation at break divided by the initial separation in the test, multiplied by 100 to give a percentage ultimate elongation.

Young's modulus. Young's modulus, or the Young modulus, is a mechanical property that measures the stiffness of a solid material. It defines the relationship between stress (force per unit area) and strain (proportional deformation) in a material in the linear elasticity regime of a uniaxial deformation. It is the Stress/Strain in this region.

Ultimate compression. The term ultimate compression refers to the amount of compression a given material can experience under a specific test method before failure occurs and the material breaks.

Average repeated elongation before failure. Refers to the number of elongations to a fixed level of elongation repeat cycles that can be performed on a test material before failure occurs and the material breaks into more than one piece.

The mechanical properties of the elastomer (Young's Modulus, Ultimate elongation, Ultimate compression, average repeated elongation before failure) are measured in a known manner using a Texture Analyzer TA.XT.Plus (Stable Micro Compositions).

For the Young's Modulus and Ultimate elongation, the elastomer is prepared as a continuous film, for example 10 Mil thick, on a release layer (for example baking paper) using a BYK square applicator or bird type film applicator (for example 5570 Single Bar 6″, 10 mils or 5357 or Square Frame 4″, 5-50 mils). If the elastomer is produced as a diluted composition, those skilled in the art will select the appropriate thickness of the drawdown film to produce a suitable film for testing. The film is left to cure at 25° C. for −24 hours or more. The elastomer is removed from the release layer and cut into rectangular sections measuring 30 mm by 10 mm using a scalpel. The thickness is then measured using a calliper to account for any shrinkage or solvent loss during curing. The rectangular film is then attached to the TA instrument within an initial separation of 12 mm. The sample is then elongated at a rate of 0.5 mm s-1 until the elastomer sample breaks. The Young's modulus is defined as the initial slope of the linear portion of the elastic region of the force-elongation curve, which occurs just after the initial force of 5 g is applied. As the initial cross-sectional area is known, the force is converted to MPa to calculate the Youngs modulus. The ultimate elongation is indicated as a percentage, i.e. extension distance at break/initial distance*100. To assess the average repeated elongation before failure, first the ultimate elongation of the sample is measured. The sample and TA instrument are arranged in the same way as to assess the ultimate elongation. The sample is then elongated at a rate of 0.5 mm s-1 to a fixed elongation of 60% of the measured ultimate elongation. The sample then returns to its original state at a rate of 0.5 mm s-1 and the cycle is repeated until the sample breaks, or until a maximum of 2000 repeat cycles.

For the Ultimate compression, the elastomer is prepared as a continuous 3 mm film on a release layer. The film is left to cure at 25° C. for −24 hours or longer. The elastomer is removed from the release layer and a series of cylindrical disks are punched out of the film with a 3.5 mm diameter. The thickness is then measured using a caliper to account for any shrinkage or solvent loss during curing. The rectangular film is then attached to the TA instrument using a compressive cycle. The sample is compressed at a speed of 0.05 mm s-1 until the sample breaks. This is observed as a rapid deflection within the stress strain graph during the compressive cycle and is clear to those skilled in the art. For all of the above mechanical property measurements results given are an average of at least 7 measurements.

Kits and Container

The film forming composition and the pretreatment composition may be maintained in separate storage compartments or in separate kit form especially if they will react together without special activation. Additionally, any catalyst/promotor/acid initiator for the film forming composition and/or pretreatment composition may be maintained separately so that it will avoid catalysis otherwise cause reaction of the alkoxysilyl groups. A convenient storage means can be utilized such as plastic squeeze tubes, plastic bottles, glass containers, sachets, multi-compartment containers, tottles, spottles syringes and plunger operated dispensing devices. Unit amounts for combination can be formulated so that the entire contents of a unit of the film forming composition can be combined with the entire contents of the catalyst/promotor for application to the keratin fibers. Alternatively, metered or calibrated dispensing containers for providing measured amounts of the components as directed by printed instructions can be provided. With some embodiments, these components can be pre-combined for storage and handling as long as a substantive constituent that would cause in situ linking is maintained in a separate compartment.

Use of the foregoing delivery means enables preparation of an embodiment for practice of the method of the present invention. This embodiment may comprise sequential, simultaneous or premixed application, to keratin fibers, of the pretreatment composition and the film forming composition. Pigment microparticles may be incorporated in the film forming composition. This aspect of application provides an underlayer of pretreatment composition and overlayer of film forming composition on the keratin fibers. Management of the medium removal, temperature of the applied compositions and use of activation agents, if any, will enable transformation to a color coating in which the polymers of these compositions in situ interact to covalently, hydrogen bond, electrostatically, coordinately, ionically, dipolar-wise and entanglement-wise connect as the completed color coating. For the film forming composition carbodiimide groups of the linker and the acid groups of the binder are chemically reactive so that covalent and/or coordinate bonds are formed between molecules of linker and binder. Also, the alkoxysilyl groups of the linker when present also combine with similar groups of the small molecule of the pretreatment composition so that the linker, binder and small molecule covalently interact to bind all constituents together. With this aspect, the resulting color coating on keratin fibers provides good remanence against repeated shampooing, rinsing and contact with mild detergents, soap and similar wash substances.

The kit forms for the pretreatment and film forming compositions may also include one or more containers or package units for the materials and/or apparatuses for practice of the Praeparatur and Fundamenta techniques. A package unit for the Praeparatur technique may include one or more containers of various concentrations and kinds of anionic surfactants as well as containers for additives such as pH adjustment and carbonate solutions. An instruction packet may also be included to direct when to use the kinds of anionic surfactant, how to dilute them, how to massage and/or work the surfactant compositions throughout the anagenic hair and how to rinse away and dry the anagenic hair after the Praeparatur treatment. A package unit for the Fundament technique may include one or more containers with various concentrations of PETT formulations as well as the carbonate base additive for preparation of the PETT formulation for use. The Fundamenta package unit may also include a cold plasma pen with associated electronics and attendant wash and rinse compositions. An instruction packet may also be included to direct how to use the PETT and/or cold plasma pen and/or oxidizer.

Application of Praeparatur and Fundamenta Techniques

According to the present invention, one or both of the Praeparatur and Fundamenta techniques may be applied to keratin fibers such as anagen hair. They may be applied separately, applied to different segments of keratin fibers, may be applied sequentially and/or may be applied simultaneously. The Praeparatur technique typically may be applied first, the anagenic hair and the Fundamenta technique may be applied as needed, and especially to the root section of anagenic hair.

The Praeparatur technique typically begins formulation of an aqueous-alcoholic surfactant with the preferred surfactant being an anionic sulfate surfactant. Using high shear mixing techniques and appropriate dilution steps, about 10 to 40 ml of a concentrated anionic surfactant mixture of sodium lauryl sulfate and sodium lauryl ether (PEG₁₀) sulfate may be combined with about 150 to 200 ml of distilled water. A mimic swatch prepared as described in the experimental section may be submersed in the detersive surfactant and briskly agitated with a fine tooth comb for several minutes. If a live salon hair model is the subject of the Praeparatur technique, they may be asked to place her head over a salon wash basin. The salon operator may then first wet the model's hair with water and then apply the surfactant solution to hair and massage and lather the Praeparatur composition onto the hair and scalp. After a period of time the salon operator may then rinse the product from the hair, and optionally repeat the process again. Depending upon the salon operator's or lab technician's visual inspection and touch of the hair, the salon operator/technician may also use a fine toothed comb or pass a hand held ultrasonic device over segments of the hair treated with surfactant solution. The process is continued with optional elevation of the anionic surfactant concentration and optional pH adjustment until the operator/technician's visual inspection and touch of the hair indicates sebum, natural oils, grime and minerals have been removed to expose bare hair shafts.

The Fundamenta technique may be applied separate, alone and independent from the Praeparatur technique or the two may be combined in either order. For a typical combined technique, the Fundamenta technique may be applied following the Praeparatur technique application.

To accomplish the Fundamenta technique, sections of the salon model's hair or sections of the mimic tress may be exposed to a device producing a cold (ambient temperature) plasma, for example a Relyon PZ2 Plasma Pen. A typical cold plasma generator passes a stream of air, nitrogen or oxygen through a high energy RF or EMF field to produce ions and with air and oxygen, also ozone. The stream of partially ionized gas may be directed toward the hair. The result is a “cold plasma” of partially ionized gas on the keratin fibers. The “cold plasma” may be splayed over and through segments of the Praeparatur treated hair to deep clean the surfaces of the hair strands. The cold plasma is applied at a suitable distance over a period of 1 to 5 minutes, preferably 1 to 3 minutes to provide the desired effect of deep cleansing.

In an alternate Fundamenta technique, an aqueous solution of at least 10 wt %, preferably at least 20 wt %, more preferably at least 30 wt % polyalkyl ammonium bromide such as of trimethyl cetyl ammonium bromide (CTAB) or trimethyl stearyl ammonium bromide (STAB) in either alkali at a pH of about 10 or in thiol at a pH above 7 is applied to the mimic hair tress or to sections of a salon model's hair and massaged throughout the tress or hair sections for a period of from about 5 minutes to 30 minutes, preferably 5 minutes to 10 minutes. This treatment is then rinsed with shampoo at acidic pH (with acetic acid) until the CT AB is removed.

In another alternate Fundamenta technique, a composition comprising 1.9 to 12% hydrogen peroxide is mixed with a persulfate bleaching composition which can be a powder. The mixed composition is applied to the hair for a period from about 1 minute to 120 minutes, more preferably from 3 to 40 minutes and then rinsed thoroughly from the hair. In an additional alternate Fundamenta technique, a composition comprising 1.9 to 12% hydrogen peroxide is mixed with a composition contain between 0.1 and 10% of an alkali agent chosen from monoethanolamine or ammonia and ammonium hydroxide. The mixed composition is applied to the hair for a period from about 1 minute to 120 minutes, more preferably from 3 to 40 minutes and then rinsed thoroughly from the hair.

Following practice of either or both of the Praeparatur and Fundamenta technique, the mimic swatch or salon model hair is ready for the Pretreatment step according to the invention.

Application of Pretreatment Composition

According to the present invention, application of the pretreatment composition to keratin fibers as a pretreatment after application of the Praeparatur and/or Fundamenta techniques and before application of the film forming composition is at least in part a factor for achievement of the qualities and characteristics of the color coating on keratin fibers. According to this embodiment of the method, the pretreatment is applied on or to at least a portion of the keratin fibers and preferably throughout the keratin fibers. The amine groups of the small molecule of the pretreatment composition are believed to interact by hydrogen bonding and dipolar interaction with complementary keratin protein groups on the keratin fibers. The alkoxysilyl groups of the small molecule of the pretreatment composition are believed to undergo condensation and to undergo condensation with corresponding alkoxysilyl groups of the linker of the film forming composition if present to form ultimately a siloxanyl polymer network intimately connected with the surfaces of the keratin fibers and interconnected with the three dimensional network of the crosslinked binder-linker. It is believed that these interactions, which are believed to involve one or more of covalent, coordinate, electrostatic, ionic, dipolar and/or entanglement combinations, function as melding between and among the keratin fibers, the pigment microparticles, and the polymers of the color coating formed from the film forming composition and the pretreatment composition.

Pretreatment with the pretreatment composition may be carried out prior to application of the color composition. Pretreatment may be carried out immediately prior to application of the color composition, or at least 1 hour prior to application of the color composition, or at least 24 hours prior to application of the film forming composition, or at least 10 days prior to application of the film forming composition, or at least one month prior to application of the film forming composition. Preferably, pretreatment may be carried out immediately prior to or within a few minutes up to an hour before application of the film forming composition. Typically, the pretreatment composition is at least partially dried with optional heating to at least substantially remove or otherwise eliminate its medium. For example, excess medium from the pretreatment composition on the hair may be removed by contacting the wet coated hair with an absorbent fabric or the wet coated hair may partially dried by heating with a hair drier. Preferably, substantial removal of the medium of the pretreatment composition is accomplished before application of the film forming composition.

In one embodiment, more than one pretreatment composition may be applied to the hair. It may be that two different pretreatment compositions are applied sequentially to provide a cumulative benefit for the subsequent film forming composition, which is then applied, or it may be that two different pretreatment and optionally two different film forming compositions are applied to substantially different portions of the hair. Such a case may arise when applying to hair which has quite different properties, for example, to sections which have been pre-bleached or color, versus natural hair, or for root versus tip hair. In such cases different pretreatments may be needed to prepare all of the hair for subsequent film forming compositions. While such different pretreatment would be directed to different portions of the hair, it is likely that there would be a least some minor mixing and some areas of the hair would receive both pretreatment compositions. A third embodiment applies where a pre-treatment composition is applied to a section of the hair, for example at the roots, and the second different pretreatment composition is then applied across all of the hair.

Application of Film Forming Composition Following Pretreatment

As described above, the one or more film forming compositions may be applied to the keratin fibers in combination with the foregoing pretreatment with the pretreatment composition. Embodiments of the film forming composition as the binder and linker components may be maintained separately until use. Application of the one or more film forming compositions to pretreated keratin fibers may be preferably accomplished by sequential application to segments of the hair. Once all segments are coated with one or more wet film forming compositions, the one or more film forming compositions may be dried and/or cured to form overlaid coating layers on the keratin fibers. Alternatively, the application and subsequent drying and or curing may be performed section by section across the head. Typically, the rate of acid-CDI addition of the film forming composition and rate of drying may be pre-adjusted through medium control, pH adjustment if needed, concentration, steric interaction, temperature, and similar factors controlling reaction and/or drying rate so that a premix of the binder and linker of the film forming composition preferably will not substantially interact before the premix is applied to the keratin fibers The practice of this step with the pretreatment embodiment initially introduces the film forming composition on top of the pretreatment layer of small molecules on the keratin fibers. Because the film forming composition is in a medium, penetration, combination, mixing and/or melding of the film forming composition into the pretreatment layer will be accomplished at least in part. The penetration is believed to enable the linking among the binder and linker of the film forming composition and the small molecules of the pretreatment composition and the keratin fibers. Drying and curing of these compositions preferably occur after all compositions have been applied. In this manner, melding among all layers is best achieved.

Application of the one or more film forming compositions to keratin fibers pretreated with the pretreatment composition is preferably carried out after pretreatment. This sequence may be carried out immediately after pretreatment, or at least 1 hour after pretreatment, or at least 24 hours after pretreatment, or at least 10 days after pretreatment, or at least one month after pretreatment.

The sequential, simultaneous or premix application of the film forming composition may be applied to at least a portion of the keratin fibers or may be applied all over the keratin fibers. The portions of the film forming composition may be applied sequentially, simultaneously in a single application over all the keratin fibers or may be applied step-by-step to the keratin fibers. Applying the film forming composition in a step-by-step manner as described above, may help to ensure that the treatable portions of the keratin fibers are saturated with the combined film forming composition and pretreatment composition and may therefore provide a better coverage of the keratin fibers.

Manipulative Techniques for Application

After each application of the pretreatment composition and one or more film forming compositions have been accomplished, and the wet coated keratin fibers, e.g. treated keratin fibers, optionally rinsed, the treated keratin fibers will begin to cure. If the treated keratin fibers are heated using an elevated temperature, the acid-CDI addition curing of the binder and linker and condensation of alkoxysilyl groups to Si—O—Si groups may be accelerated. The temperature of the keratin fibers can be increased to elevated temperatures above room temperature such as 40° C. or higher, for example using a hair drier. While the keratin fibers are being heated, some form of interdigitated implement can be used to help separate portions of the keratin fibers, and especially separate hair strands from one another. Examples of interdigitated devices include a comb or a brush. The keratin fibers can be heated with a hair drier while simultaneously being combed or brushed until it is dry to the touch. Alternatively, other means can be employed to heat and separate the keratin fibers such as hair simultaneously. For example, using a combination of air movement and vibrations will accomplish distribution of the multicomponent composition throughout the strands of hair.

Operational Method for Coating Hair

The performance of operational method aspects of the present invention can be applied to keratin fibers to form a coating of the pretreatment and film forming compositions and optional topcoat composition. This aspect of the invention concerns a method for coloring keratin fibers and comprises applying embodiments of one or more pretreatment and film forming compositions for a time sufficient to deposit an effective color coating on the keratin fibers such as each keratin fiber or hair strand. A somewhat to substantially overall distribution of the coating on the length and circumference of each fiber is produced.

To accomplish this aspect, after performing the Praeparatur and/or Fundamenta techniques to prepare the keratin fibers for acceptance of the pretreatment and film forming composition, embodiments of the pretreatment and film forming compositions are applied to the keratin fibers according to the sequences described above by brushing, painting, spraying, atomizing, squeezing, printing, rubbing massaging or in some manner coating the keratin fibers such as hair strands with the embodiments. Following application of a compositional embodiment to the keratin fibers such as hair strands, the composition is set, cured, linked, coordinated and/or otherwise melded together preferably by warming with blown warm air from a hair dryer or similarly treatable to remove the medium, initiate acid-CDI addition and condensation of the alkoxysilyl groups as well as hydrogen bonding, molecular entwining and polar interactions among the binder-linker polymer, the in situ formed silicone network formed from the small molecules of the pretreatment composition and keratin fibers. The setting leaves a substantial to essentially complete overall bonding and binding among these substantive constituents of the color coating on keratin fibers.

The rate or rate of reaction for the film forming composition and pretreatment composition to cure and to bond internally and with each other is the speed at which reactants are converted into products. In the context of the film forming and pretreatment compositions forming adherent colored coatings, the rate refers to the speed at which the covalent and non-covalent bonding occurs. In one embodiment it is preferred that the rate of reaction/drying is not so fast that the resulting elastomer forms before the wetting and spreading on keratinous surface can occur. If the rate of reaction/drying is too fast the resulting elastomer may not then be able to subsequently wet and spread on the hair surface, resulting in an inferior coating of the hair and one that displays less resistance to washing. In contrast, a rate of reaction/drying that is extremely slow will not enable a practical result in typical times for salon coloration treatment. In a preferred embodiment the rate of reaction/drying is slow enough such that the film forming and pretreatment compositions can wet and spread on the keratinous surface, yet also fast enough that a macroscopically continuous film on a keratinous surface is formed as the film bonds/binds covalently/non-covalently. The typical period for accomplishing continuous film formation is preferably less than 48 hours, more preferably in less than 24 hours, even more preferable in less than 12 hours, most preferable in less than 6 hours and especially most preferably in less than 30 minutes following the completion of application and under normal room temperature conditions.

The bonding and binding of the substantive constituents of pretreatment and one or more film forming compositions and the keratin fibers during application provides a color coating that resists removal by washing with dilute mixtures of soap and water or shampoo and water. Color remanence is developed so that washing with dilute aqueous soap solution or dilute aqueous shampoo will not substantially remove the coating, but the coating can be facilely removed by use of a transformation trigger. The properties of the coating include remanence, flexibility, adhesion, abrasion resistance and remanence which are due at least in part to the binding and bonding character of the substantive coating constituents including at least their intermolecular entwining, ionic and electrostatic intermolecular interaction, covalent and/or non-covalent linking, hydrogen bonding, dipole interaction and lipophilic interaction of these substantive constituents.

The pretreatment and film forming compositions and optional topcoat in accordance with the present disclosure can have a viscosity that can be controlled to enable the product to be applied to the hair using either a brush and bowl or a bottle, but with sufficient rheology such that it does not drip and run from the hair onto the face or body.

Alternatively, low viscosity formulations may be applied to the hair via a suitable application device such that it does not drip and run form the hair onto the face and body.

The pretreatment and film forming compositions and optional topcoat can be utilized in concentrated form or in serial dilutions, to provide for a consistent color results substantially along the entire length of the keratin fibers.

The aspect of coloring keratin fibers with a pretreatment and film forming composition and optional topcoat as described above includes a method for this coloring. The method comprises:

(i) applying the above-described pretreatment and film forming compositions to keratin fibers to obtain an effective, deposited coloring amount of the color composition including pigment microparticles and optional additional components; (ii) setting the pretreatment and film forming compositions by removing or otherwise eliminating the medium (e.g., by drying the composition); and (iii) setting the interaction among the reactive constituents of the film forming and pretreatment compositions by initiating the in situ linking among these groups.

During the setting/drying step, color distribution can be facilitated by concurrently moving and/or stroking the hair with an interdigitating device. Interdigitating devices include a comb or brush. The interdigitating device needs to be pulled substantially along the hair strands from root to tip. It can be pulled through at a rate of 0.1 cm s⁻¹ to 50 cm s⁻¹ or at a rate between 0.5 cm s⁻¹ to 20 cm s⁻¹.

The pretreatment and film forming compositions and optional topcoat are applied to the keratin fibers in any suitable way including spraying the pretreatment and film forming composition, massaging the keratin fibers by hand, after applying the pretreatment and film forming composition to the hand or by combing, brushing or otherwise applying the pretreatment and film forming composition throughout the keratin fibers.

The methods by which the pretreatment and film forming compositions and optional topcoat composition described herein are applied can be modified, such that the user applies the product in one region of the hair, and then can apply a diluted version in another region of the hair. The dilution formula is specially chosen to be compatible with the colorant formulation and reduces the coloring strength, while maintaining the longevity of the color result. This can effectively be a “blank” formulation, which contains broadly the same materials as the coloring formulation, but with lower or no pigments present. When diluted the ratio of the diluent to colorant can be between about 10:1 and about 1:10, about 8:1 and about 1:2 or about 5:1 and about 1:1.

Alternatively, the amounts of pretreatment and film forming compositions and optional topcoat composition applied can be altered in different regions of the hair, for example half the product is applied in the lengths of the hair, leading to a less colorful result. The difference in amounts applied in one region of the hair versus another can be between about 4:1 and about 1:4 or about 2:1 and about 1:2.

Alternatively, a combination of this approaches may be used to deliver the target color variation.

When the foregoing techniques are not possible to be applied, rather than apply a single hair color, it may be possible to apply two or more hair colors to different regions of the hair. When this is done, the different hair colors preferably provide complimentary colors so as to develop an attractive result. The difference in colors that can be used, based on the end result on hair tresses (as described later—untreated hair tresses) are as follows. As described within the CIELCh composition:

Color 1 (LCh) versus Color 2 (LCh)

Color 1 L-15<Color 2 L<Color 1 L+15 0 or Color 1 C-10<Color 2 C<Color 1 C+10

Color 1 h-45<Color 2 h<Color 1 h+45

Those skilled in the art of color measurements will know how to interpret difference in hue angles, h, when they extend from low positive values to those near to 360 degrees due to the periodic circular nature of the hue angle.

The method for use of the pretreatment and film forming compositions and optional topcoat composition in accordance with the present invention can occur during any suitable period. The period of application can be from about 0 to 30 minutes, but in any event a period that is sufficiently long to permit the coating of pigment microparticles to coat and adhere or bind to each separate keratin fiber, substantially along the entire length of each keratin fiber. The resultant is keratin fibers having a color and permanence that is at least equivalent to the color resulting from oxidative hair color, except under much milder conditions.

The pretreatment and film forming compositions described herein can be prepared by the manufacturer as a full shade, e.g., one that is ready to apply to the hair, and then shipped as a discrete unit to the user. The user may need to re-blend the pretreatment and film forming composition prior to application to ensure that the pretreatment and film forming composition delivers the optimum performance. Such re-blending can require shaking the pretreatment and film forming composition for about 1 to about 120 seconds or from about 3 to about 60 seconds. Re-blending may also be performed by stirring the pretreatment and film forming composition prior to use. This may occur for about 1 to about 120 seconds or from about 3 to about 60 seconds. Although the pretreatment and film forming compositions according to the present invention are designed to provide stable suspensions of the pigment particles, the re-blending to agitate the microparticles and resuspend them in a substantially uniform distribution is desirable.

Multiple compositions comprising different pigments can be blended together prior to application to the keratin fibers. Such blending can be done in a manner so as to apply a plurality of complementary surface colors to the keratin fibers. Typically, a large group of different pigments with small molecule coatings and concentrated in dispersant media are provided as pre-mixes for combining with the film forming composition. The color selection program describe above will determine which selections of the different pigment concentrates will provide the desired color result for the customer's hair. The pre-mixes are metered into the film forming composition at concentrations ready for application to anagenic hair.

The pretreatment and film forming compositions can include multiple layers, involving multiple applications of the film forming composition following the first application of the pretreatment and film forming compositions. It may be beneficial also to periodically reapply the third component. The techniques for applying multiple layers follow the techniques described above for application of a single pretreatment and color composition.

The coating of pigment microparticles comprising at least one pigment in a coating of the substantive constituents of the pretreatment and film forming compositions can be adhered to the treatable material such as hair utilizing a coating having a total thickness at any given point along the hair fiber of less than about 5 μm, preferably less than about 2 μm as measured using a scanning electron microscope (SEM). To make such measurements, a coated hair sample can be embedded in a suitable resin, and then sectioned root to tip using techniques known to those skilled in the art of scanning electron microscopy. The thickness of the layer on the surface can then be assessed along the line of cuticles over a length of at least 100 μm. The thickness of layer is determined by averaging 10 points evenly spaced over the section of interest.

In the course of application of the pretreatment, film forming compositions and optional topcoat composition, it is possible to dress portions of hair rather than as one whole uniform area from root to tip and across the regions of the scalp. Several nonlimiting examples help explain a few of the many possible portions of the hair. In a first example the first portion of the hair refers to the hair adjacent to the persons scalp, the so called root hair region which may extend from a few millimeters to several centimeters. In this example the second portion of the hair is not adjacent to the scalp, i.e., the area which is not within the first portion. There may be some overlap between the first and second portions, due to the limitations of physically segregating these two portions on a person's head, but the two portions are different to one another. In a second example, the first portion of the hair refers to the one whole uniform area from root to tip. In this example, the second portion of the hair is then another section of hair from root to tip. These two portions are different to one another, but have a significant area of overlap, with the second portion covering an area which may to some extent overlap with the first portion.

This understanding of the different qualities and attributes of sections of hair on a person's scalp shows that it is appropriate and preferably to apply separately pretreatment and color compositions to sections of hair strands. In addition to varying the concentration of the pigment microparticles and optional coloring agent, different shades and/or colors of pretreatment and film forming compositions can be applied to different sections of a strand of hair or a group of strands of hair. For example, the hair roots, mid sections and tips sometimes or often have different shades of color in their natural condition. This variation can be mimicked, altered or covered through use of differing shades or colors of the pretreatment and film forming compositions. Roots, for example can be covered with a lighter shade and the tips can be covered with a darker shade to produce a two tone variation of the hair. Application to the hair of a first portion of pretreatment and film forming composition followed by stripping the composition from the hair mid sections and ends followed by setting the remaining composition on the hair roots will provide a first hair color coating on the roots. The mid-sections and tips can be dipped or brush applied with a second portion of pretreatment and film forming composition to complete the two color or two tone treatment. The use of multiple pretreatment and film forming compositions to produce multiple coatings on the hair can provide overlapping, sequential or coterminous coatings on the hair according to typical and routine techniques for applying multiple versions of hair color practiced by professional hair salons.

Post Treatment

An optional post treatment composition can be applied after treating the keratin fibers with the pretreatment and film forming compositions described herein. This can be applied either directly after completion of coloring with these compositions. The post treatment can be either single application or multiple application across time. The post treatment can be used to improve one or more of: feel, resistance to shampoo/conditioner/water washing treatments, and shine of the hair. Nonlimiting examples of materials used to improve the feel are those which impart lubricity to the treatable material such as hair strands and/or help the hair strands separate during the drying steps. These materials include, for example silicone conditioners, silicone polyethers, silicone polyglucose, polyisobutene, copolymers of ethylene and propylene oxide, and commonly used cosmetic oils and waxes. Nonlimiting examples of materials used to improve shampoo wash resistance are materials which act as a ‘sacrificial layer’ for example polymeric silicones and their copolymers, silicone resins, cosmetics oils and waxes. Nonlimiting examples of materials used to improve the shine of hair (meaning a decrease of the full width at half maximum parameter of the specular reflection curve as measured by a goniophotometer) are those materials which form a smooth film above the previously applied pigment polymer composite on the hair. In general, any cosmetically known film forming material can be used, but preferred are materials such as polymeric silicones and polycationic materials.

Removal of Color Coating

Hair colorants made from the pretreatment and film forming composition are very resistant to everyday hair treatments (such as washing with shampoo, conditioner etc) can be removed via use of specifically designed “removal formulations.” These are specific chemical mixtures, described herein, and are designed to work by one or both of two broad mechanisms: cleavage of chemical bonds, either linking groups in the binder of the film forming composition and solvation of components of the colored coating.

First, the mixture can be made to be a solvent for the pigment itself. In this case, the mechanism of removal involves first dissolution of the pigment from the binding matrix, followed by removal from the hair by rinsing with water or some other carrier. In this case it is believed, whilst not being bound by theory, that the chemical nature of the pigment, even when in dissolved form, is such that there is minimal attraction/solubility in the hair matrix itself, thus allowing removal of the color.

Second, the “removal formulation” can be made such that it dissolves, weakens or chemically breaks down the polymer coating holding the pigment on the hair. In this case it is believed, whilst not being bound by theory, that the pigments embedded in the binder matrix are released due to weakening or dissolution of the coating itself and, because the coloring material is a pigment, it has minimal attraction for the hair surface and is too big to penetrate the hair, and in consequence this facilitates removal of the color.

The combination of the above mechanisms will also provide the desired result of removal of the color.

Attacking the functional group bonds of the polymer network of the coating on the treatable material such as hair can have a dramatic impact on the properties of the coating which is adhered to the surface. An agent that cleaves those bonds can act as a trigger agent to divide the polymeric network and enable surfactant and solvent to readily disperse the cleaved coating. Such agents include basic amino alcohols such as dimethylaminoethanol (dimethylethanolamine, DMEA), dimethylaminopropanol, and similar amino alkanol agents such as monoethanolamine, diethanolamine and triethanolamine. These amino alcohols can be formulated in aqueous medium to enable coating removal. Additionally, or alternatively, fatty organic acids such as dodecylbenzene sulfonic acid or oleic acid may be combined with non-aqueous medium such as a volatile hydrocarbon including but not limited to dodecane to trigger removal. These organic acids function as surfactants to lift the coating from the keratin fiber surfaces and to break the functional group bonds which cleaves the polymeric network of the coating. The concentration of the trigger agent in alcoholic medium such as methanol, ethanol or aqueous medium or in non-aqueous medium may range from about 0.1% to about 15% by weight, preferably about 0.5% to about 10% by weight, more preferably about 1% to about 7.5% by weight relative to the total weight of the removal solution.

The binder with acid-CDI links may also contain a group such as an ester, amide, urea or urethan group which can function as a cleavable linkage. This linkage is susceptible to hydrolysis and can be cleaved using basic or acid lysis. The cleavage will include a counter-nucleophile which can be water or a small molecular weight monofunctional amine or thiol.

The organic or silicone polymer having chain extensions with siloxane condensation, a strong acid such as dodecyl benzene sulfonic acid (DBSA) or a source of fluoride anion tetrabutylammonium fluoride (TBAF) in appropriate solvent as described in combination with Hansen solubility parameters including δd+δp+δh wherein δd is from 13 to 25, preferably 15-19 and δp is from 0 to 15, preferably 0 to 5 and δh is from 0 to 25, preferably 0 to 8.

Additionally, the in chain functional groups such as N-acylurea, urea, urethane, amide and/or ester can be cleaved through use of a small molecular weight monofunctional amine or thiol to attack the functional group and disrupt polymer chains.

Also, if silicone polymeric bridges are present in the silicone polymer or in the organic polymer, an organic acid (such as DBSA) may be used to de-polymerize the chain. TBAF or other organic fluoride such as Olaflur can also be used to de-polymerize the chain. It is also advantageous in all “off” techniques to employ an off reagent also has some surfactant quality.

When the pretreatment and film forming composition is applied to the hair, the multi-application process physically distributes the components to cover all of the hair. The spraying, massaging, combing and/or hand manipulating the pretreatment and film forming compositions produces the full coverage and at the same time leaves thin spots in the otherwise substantially uniform coating. This activity also will aid in the removal process.

Additionally, waxy non-reactive, non-combinable substances having melting points somewhat higher than human body temperature may be incorporated into the pretreatment composition. The concentration of waxy substance may be sufficient to enable heat disruption of the polymer film of the pretreatment layer on the keratin fibers but not enough to prevent the engagement of the polymer film properties of the pretreatment layer. By warming the hair with a hair dryer at a temperature of more than somewhat higher than body temperature, the waxy substance may be melted at least in part so as to disrupt the color coating on the keratin fibers. Combing or brushing can remove disrupted color coating.

Alternatively, an organic solvent soluble polymer such as a cellulose derivative, including but not limited to nitrocellulose, cellulose acetate-butyrate or other solvent soluble polymer may be incorporated into the film forming composition. The amounts and concentrations of the solvent soluble polymer are sufficient to enable the polymer to form separate domains of polymer film within the coating produced from film forming compositions. Contacting such a coating with an organic solvent in aqueous medium will at least in part dissolve the solvent soluble polymer and disrupt the continuous nature of the coating layer. Combing or brushing can remove disrupted color coating.

Remanence and Treatable Material Inspection

Damage caused to the hair by application of the pretreatment and film forming composition and removal of the resulting coating can be assessed by FT-IR (Fourier Transform Infrared) method, which has been established to be suitable for studying the effects of keratin surface damage. Strassburger, J., J. Soc. Cosmet Chem., 36, 61-74 (1985); Joy, M. & Lewis, D. M., Int. J. Cosmet. Sci., 13, 249-261 (1991); Signori, V. and Lewis, D. M., Int. J. Cosmet. Sci., 19, 1-13 (1997)). In particular, these authors have shown that the method is suitable for quantifying the amount of cysteic acid. In general, the oxidation of cystine is thought to be a suitable marker by which to monitor the overall oxidation of the keratinous part of the fiber. Net, the measurement of cysteic acid units by FT-IR is commonly used.

Signori and Lewis (D. M., Int. J. Cosmet. Sci., 19, 1-13 (1997)) have shown that FT-IR using a diamond Attenuated Total Internal Reflection (ATR) cell is a sensitive and reproducible way of measuring the cysteic acid content of single fibers and bundles. Hence, the method that can be employed to measure the cysteic acid content of multiple fiber bundles and full hair switches, is based upon the FTIR diamond cell ATR method employed by Signori and Lewis (1997). The detailed description of the method for testing the different damage inhibitors follows thereafter:

A Perkin Elmer Spectrum® 1 Fourier Transform Infrared (FTIR) composition equipped with a diamond Attenuated Total Internal Reflection (ATR) cell may be used to measure the cysteic acid concentration in mammalian or synthetic hair. In this method, hair switches of various sizes and colors can be used. The switches may be platted (˜1 plait per cm) in order to minimize variations in surface area of contact between readings. The Oxidative hair Treatment Protocol described above may be repeated for 5 cycles to mimic the behavior of hair after repeated bleaching cycles. Following this treatment, four readings per switch may be taken (⅓ and ⅔s down the switch on both sides), and an average calculated. Backgrounds may be collected every 4 readings, and an ATR cell pressure of 1 N/m may be employed. The cell may be cleaned with ethanol between each reading, and a contamination check may be performed using the monitor ratio mode of the instrument. As prescribed by Signori &amp; Lewis in 1997, a normalized double derivative analysis routine may be used. The original spectra may be initially converted to absorbance, before being normalized to the 1450 cm⁻1 band (the characteristic and invariant protein CH₂ stretch). This normalized absorbance may be then twice derivatized using a 13 point averaging. The value of the 1450 cm⁻¹ normalized 2nd derivative of the absorbance at 1040 cm⁻¹ may be taken as the relative concentration of cysteic acid. This figure may be multiplied by −1×10⁻⁴ to recast it into suitable units.

When the compositions of the current invention can be applied to the hair and then removed there can be a non-significant change to the level of damage to the hair, whereas with conventional oxidative colorants there can be a large increase in the measured damage.

The instant disclosure is not limited in scope by the specific compositions and methods described herein, since these embodiments are intended as illustration of several aspects of the disclosure. Any equivalents are intended to be within the scope of this disclosure. Indeed, various modifications in addition to those shown and described herein can be within the grasp of those with ordinary skill in the art. Such modifications are also intended to fall within the scope of the appended claims.

Color Selection

Also contemplated herein are pretreatment and film forming compositions having a given color area (gamut principle described above) defined by color coordinates (a*, b*) in the color space represented by the L*a*b* color composition, which can be divided into a plurality of color areas. Each of the plurality of colors obtained from the area surrounding a given set of hair fibers is judged to belong to which color area of the colored area of a certain color. The number of colors judged for each color area is counted, and the color of the color area with the largest number of colors is selected as a representative color of the area surrounding a given set of hair fibers. The compositions are capable of delivering colors on hair (test method herein for fade) such that the results colors lie within the range of about 18<L<about 81, about −2<a<about 45, and about −13<b<about 70.

When the color is removed from the keratin fibers the waste water/composition can be treatable to remove the pigments from the waste water effluent composition. This can be achieved by filtration, or through cyclone technology, where the density differences are used to force the pigments to the settle, and the water to pass through.

Salon Demonstration Regarding Anagenic Hair

Remanent Differences Between Hair Tresses and Anagenic Hair

The following SALON example demonstrated the difference in performance observed between the lab using regular untreated and treated hair tresses and when the same products were tested within a test salon on anagenic hair on models' or panelists' heads. The following compositions were used.

Pretreatment Composition (PS1):

Concentration Material Name Supplier (w/w %) PEI¹ Epomin P-1050 (MW Nippon Shukobai 1 70.000) Preservative Phenoxyethanol 1 Medium Water Q.S. to 100 ¹polyethyleneimine

Coloring Composition (S1A)

Material Name Supplier w/w % w/w % Crosslinker PERMUTEX ® Stahl 2.00    2.00    XR-13-554 Holdings B.V. Polymer Belsil P1101 Wacker 10.0 10.0% (50% active) Chemie (5% active) (5% active) AG Pigment Hostaperm Pink E Clariant 1.00 1.00 Red 122 AG Alkali Ammonium to pH 8.5 to pH 8.5 Hydroxide (25%) Dispersing Solsperse W100 Lubrizol 0.50% 0.50% agent Solvent/ 2-butoxy ethanol Sigma- 2.00% 2.00% Plasticiser Aldrich Solvent/ Ethanol Sigma q.s. to q.s. to Medium Aldrich 100% 100%

On the tresses, the coloration products were applied using the protocols described in the following experimental sections. For the salon testing, the same protocols were applied. The compositions were not applied to the whole of the models' head, discrete strands were selected, similar in width to a hair tress upon which the product was applied. This technique enabled the use of two difference coloration products on the same panelist's head on two spatially resolved strands of hair. After the coloration product was applied and dried, a short while later the model's hair was rinsed with water and then dried again.

The color remanence was performed after 15 wash cycles on the lab tresses and after the models had performed 15 wash cycles using their regular washing and grooming habits.

Salon Experiment Number: Salon1 Salon2 Pretreatment Composition: None PS1 Coloring Composition: S1A S1A Results on lab strands Untreated Hair +++ +++ Treated Hair +++ +++ Results on anagen hair Panelist 1 0 0 Panelist 2 ++ + Panelist 3 ++ ++ Panelist 4 + + Panelist 5 ++ +

The results showed that on lab tresses, on untreated and treated hair the color remanence was very strong for both composition combinations tested, Salon1 without the pretreatment composition and Salon2 where the pretreatment composition was applied.

In contrast, on the 5 models (or panelists) within the salon test, the performance varied heavily from strong to weak. Even when the performance was strong this was an average assessment, and the results were always weak for all panelists when considering the root hair, the first few centimeters of hair adjacent to the scalp. Generally, color remanence was better on panelists with hair that had been previously lightened or bleached. Those with the least treated hair had the poorest performance.

These results from the testing on tresses and on anagenic hair on panelists of the same products highlights the considerable challenges to provide long lasting remanent colored films on the outside of the hair fibers on real consumers hair. These challenges are most noticeable on the “roots”, hair which is adjacent to the scalp.

The same results were also obtained from a similar salon test using a film forming composition of isopropanol, pigment, polysilicone with pendant α,β unsaturated carboxyl groups having a weight average molecular weight of approximately 0.5 to 0.8 KDa, a polysilicone with pendant alkyl amine groups and terminal triethoxy silyl groups having a weight average molecular weight of approximately 0.5 to 0.8 KDa, and a pretreatment composition of APTES in isopropanol, water and acetic acid.

EXPERIMENTAL SECTION Examples General

The color compositions described herein within the examples are generally applied to a hair tress. One gram of each of the pretreatment composition and/or film forming composition is applied to each gram of hair tress. The tress is placed on a flat plate or in a bowl and the pretreatment composition and/or film forming composition brushed into the hair to ensure that all of the strands look visibly coated with the composition(s). The hair tress is then dried by heating with a hair dryer while combing until it is dry to the touch and the hairs are individualized.

Praeparatur and Application of Film Forming Systems to Color Hair:

The compositions used herein are prepared as described in the following sections prior to starting the applications steps.

General Description of Treatment and Application of Color Composition Steps:

-   -   If required such as with Sebum Insult and/or mimic hair, apply         at least one Praeparatur composition to the hair tresses and         then rinse the hair strands. Repeat as required.     -   If required such as with Sebum Insult and/or mimic hair, perform         a Fundamenta step on the hair tresses.     -   Apply at least one Pre-treatment composition to the hair         tresses.     -   Application of film forming composition to hair tresses followed         by curing to produce colored hair tresses.

After the color composition is applied to the hair tress one of the following is then performed to assess performance:

-   -   Standard color remanence test     -   Sebum Insult test     -   Full root simulation color remanence test     -   Color removal procedure

Standard color remanence procedure: The standard color remanence procedure is used to determine the remanence of the colored hair tresses.

-   -   1. Rinse the colored hair tress for approximately 10 seconds         with water (4 L min′) at approximately 37+/−3° C.     -   2. Apply 0.1 g “Wella Professional Brilliance Shampoo for fine         and normal hair” without dilution to the individual colored hair         tress weighing about 1 g described above.     -   3. Shampoo is worked into the colored hair tress for about 30         sec with fingers by using a stroking motion into the hair.     -   4. The shampooed colored hair tress is rinsed with water for         approximately 30 seconds.     -   5. The rinsed colored hair tress is then dried using a hot blow         dryer while mechanically separating the fibers using a comb         until uniformly dry.

Steps 1-5 described above represents one cycle of the standard color remanence procedure. Within the following experiment sections the standard remanence cycle is repeated 15 times, giving a total of 15 cycles of shampoo applications. The visual color remanence assessment, described below, is then performed to assess the color remanence after the standard color remanence test.

Sebum Insult Test: This test was used to determine the color remanence of the hair coated with a multicomponent coloring composition under more demanding conditions which are designed to better mimic consumers root hair which gets replenished with sebum. Versus the standard color remanence test two changes are made. Rather than using standard natural white hair tresses, the untreated light blonde hair tresses are used (untreated tresses). Some instances of the untreated tresses undergo a Praeparatur and/or Fundamenta techniques as required by the experimental procedure but the untreated tresses are not precoated with sebum. The untreated tresses which in some instances have been processed with the Praeparatur and/or Fundamenta techniques are then colored with the pretreatment and film forming compositions to produce the color coating to the tresses. The color coated tresses are then cycled through the following Sebum Insult protocol to mimic the recoating of the hair with sebum originating from the scalp in-between hair washes.

Steps to apply the color composition (pretreatment and film forming compositions) to the Sebum Insult hair tress are performed as described above. The color coating on the Sebum Insult hair tress is then allowed to rest at 20° C. and 60-70% RH for 20 hours. This lower temperature is chosen to more closely replicate conditions on a consumer hair.

Remanence Procedure for Sebum Insult Test

After 20 hours, the following sebum and shampoo sequence was performed upon the Sebum Insult hair tress with color coating.

1. Apply 0.1 g of synthetic sebum to the colored Sebum Insult hair tress weighing about 1 g described above. The sebum is rubbed into the tress to distribute it evenly. 2. Place the tress in the oven at 40° C. for 30 min. 3. Rinse the hair tress for approximately 10 seconds with water (4 L min′) at approximately 37+/−3° C. 4. Apply 0.1 g “Wella Professional Brilliance Shampoo for fine and normal hair” without dilution to the colored mimic hair tress weighing about 1 g described above. 5. Shampoo is worked into the colored Sebum Insult hair tress for about 30 sec with fingers by using a stroking motion into the hair. 6. The shampooed colored Sebum Insult hair tress is rinsed with water for approximately 30 seconds. 7. Apply 0.1 g “Wella Professional Brilliance Shampoo for fine and normal hair” without dilution to the individual colored Sebum Insult hair tress weighing about 1 g described above. 8. Shampoo is worked into the colored Sebum Insult hair tress for about 30 sec with fingers by using a stroking motion into the hair. 9. The shampooed colored Sebum Insult hair tress is rinsed with water for approximately 30 seconds. 10. The rinsed colored Sebum Insult hair tress is then dried using a hot blow dryer while mechanically separating the fibers in the substrate material until uniformly dry.

Steps 1-10 described above represent one cycle of the Sebum Insult color remanence test. These are repeated for a total of 5 cycles. As in the standard color remanence test, Sebum Insult test results in a total of 10 shampoo applications to the hair tress prior to assessment. The visual color remanence assessment described below is then performed to assess the color remanence after the Sebum Insult color remanence test.

Full root simulation color remanence test: This test was used to determine the color remanence of the hair coated with a multicomponent coloring composition under more demanding conditions which are designed to better mimic a person's anagenic hair and especially a person's root hair. Versus the standard color remanence test three changes are made. Rather than using standard natural white hair tresses, light blonde hair tresses are used (untreated tresses). Prior to application of a color composition (pretreatment and film forming compositions) to the tresses, a sebum mimic is applied to the tresses to account for the anagenic hair with sebum. The sebum coated tresses in some instances are then processed with the Praeparatur and/or Fundamenta techniques. The tresses ae then coated with the pretreatment and film forming compositions and cured to produce colored tresses. The colored tresses are washed using an extended protocol including reapplication of sebum mimic to imitate the recoating of the hair with sebum originating from the sebaceous glands in-between hair washes. The full root simulation hair tress is termed mimic hair or mimic hair tress throughout this application. A synonym also used in this application to describe mimic hair is “full root simulation hair.”

The following procedure describes initial sebum application to produce mimic hair. The light blonde hair tresses are treated with synthetic sebum to better simulate root hair found on a person. Sebum measuring 0.1 g of (Hautfett nach BEY, sold by Wfk-Testgewebe GmbH) is applied to the individual hair tress weighing about 1 g described above. The tress was placed in an over at 40° C. for 30 minutes to produce a mimic hair tress. The mimic hair tress is then optionally subjected to the Praeparatur and/or Fundamenta techniques and processed to produce the colored tresses as described above.

After 20 hours, the following sebum and shampoo sequence was performed upon the Mimi hair tress with color coating.

1. Apply 0.1 g of synthetic sebum to the colored mimic hair tress weighing about 1 g described above. The sebum is rubbed into the tress to distribute it evenly. 2. Place the tress in the oven at 40° C. for 30 min. 3. Rinse the hair tress for approximately 10 seconds with water (4 L min′) at approximately 37+/−3° C. 4. Apply 0.1 g “Wella Professional Brilliance Shampoo for fine and normal hair” without dilution to the colored mimic hair tress weighing about 1 g described above. 5. Shampoo is worked into the colored mimic hair tress for about 30 sec with fingers by using a stroking motion into the hair. 6. The shampooed colored mimic hair tress is rinsed with water for approximately 30 seconds. 7. Apply 0.1 g “Wella Professional Brilliance Shampoo for fine and normal hair” without dilution to the individual colored mimic hair tress weighing about 1 g described above. 8. Shampoo is worked into the colored mimic hair tress for about 30 sec with fingers by using a stroking motion into the hair. 9. The shampooed colored mimic hair tress is rinsed with water for approximately 30 seconds. 10. The rinsed colored mimic hair tress is then dried using a hot blow dryer while mechanically separating the fibers in the substrate material until uniformly dry.

Steps 1-10 described above represent one cycle of the full root simulation color remanence test. These are repeated for a total of 5 cycles. As in the standard color remanence test, full root test results in a total of 10 shampoo applications to the hair tress prior to assessment. The visual color remanence assessment described below is then performed to assess the color remanence after the Sebum Insult color remanence test.

Color Remanence Assessment

Remanence was assessed visually by comparing the washed samples versus a retained tress which had been colored but not washed. Color remanence was graded as either very strong when the color after washing was either unchanged or remaining very intense, strong where the color remained intense but was noticeably less than the starting color, moderate where the color was still visible but obviously less than the starting color or weak where none or a low level of color. To simplify the results tables shown below they were giving the following annotations, very strong=+++, strong=++ and moderate=+, weak=0.

Hair tresses used for testing. Three types of hair were used to mimic consumers hair from their tips to their roots.

-   -   Treated hair tresses. These were tresses which were subjested to         the following treatment to reflect consumers tip hair: Natural         white undamaged human hair was purchased (Kerling International         Haarfabrik GmbH, Backnang, Germany) in the form of 10 cm long         and 1 cm wide tresses. The tress was treated with a mixture of         Blondor Multi-Blonde bleach powder available from Wella         Professionals mixed 1 part with 1.5 parts of 12% Welloxon         Perfect available from Wella Professionals. About 4 g of this         mixture was applied to each gram of hair. The tresses were then         incubated in an oven at 45° C. for 30 minutes after which they         were rinsed in water, 37+−3° C. with a flow rate of 4 L/min for         2 minutes and the hair was then dried with a standard Hair dryer         from Wella.     -   Untreated hair tresses. These were used to reflect mid length         consumer hair. The Natural white undamaged human hair described         above was used as received. Additionally, in some procedure         light blonde hair was purchased (Farbe 9/0 from Kerling         International Haarfabrik GmbH, Backnang, Germany) in the form of         10 cm long, 1 cm wide strands. The light blonde hair has in         prior testing been shown to be a better mimic of consumers root         hair, the hair adjacent to the scalp. Whilst not wishing to be         bound to theory, it is thought to be less processed by the         supplier prior to preparing hair tresses than the natural white         hair tresses. These hair tresses were also used as received.     -   Mimic hair tresses. These are the untreated hair tresses to         which synthetic sebum is applied and distributed throughout the         hair strands as described above in the section titled Full root         simulation color remanence test. To simulate the continued sebum         secretions of anagenic hair, the synthetic sebum composition is         reapplied to the color coated mimic hair tress after each         shampoo of the remanent testing.     -   Sebum Insult hair tresses. These are untreated hair tresses         which are colored without first receiving a sebum treatment.         Following formation of a color coating on the tresses, they are         subjected to a sebum coating and dried each time before being         subjected to the shampoo cycle.     -   Untreated hair tresses as purchased and as used are not coated         with natural or synthetic sebum, but they do have the F layer         coating. Mimic hair tresses are coated with synthetic sebum and         have the F layer coating as a result of the use of the untreated         hair tresses as the starting material for the mimic hair         tresses.

Fundamenta Procedures. Two different Fundamenta procedures were performed separately on the hair. In both cases, the procedure was performed on the hair which first had the Praeparatur step described above.

Plasma Fundamenta procedure. An atmospheric low temperature plasma pen, Piezobrush® PZ2 (Relyon Plasma, Regensburg, Germany) was used to treat the hair tress. It was held 5 mm from the tress surface and moved slowly up and down along the tress for 3 minutes on each side to perform the Fundamenta step.

Alkali Cleaning Fundamenta procedure. The following solution was prepared, CTAB (details) 0.20%, sodium carbonate, 1.60% and water 98.2%. 50 g of solution was prepared for each tress that was treated in a beaker. This was heated (39° C. to 60° C.). The tresses were placed in the alkaline surfactant solution for (longer time for lower temperature, 15 min to 30 min) with stirring performed by a magnetic stirrer. Afterwards tresses were removed from the surfactant solution and dried. The following acidic cleaning composition was then prepared. Texapon N70 (70% in Water) 14.29%, Isopropanol 25.00%, Acetic acid 3.00%, Water 57.71%. The following steps were then performed.

1. Rinse the treated hair tresses thoroughly for 2 minutes with water (4 L min⁻¹) at approximately 37+/−3° C. 2. Apply acidic cleaning composition to hair, using 0.1 g for each gram of hair tress for 60 seconds with the finger to distributed through the hair tress. 3. Rinse the hair swatch with water for 60 sec with water (4 L min⁻¹) at approximately 37+/−3° C. 4. Repeat steps 2-3 two more times. 5. Blow dry tresses.

Pigment Red 122 Paste

The pigment is combined with isopropanol and a dispersant and blended using a bead mill.

Pigment red 122 paste ingredients Pigment paste (wt %) Pigment red 122 10 Disperbyk 140 5 Isopropanol Qs to 100

Example 1. Performance of the Film Forming Systems on Hair which has Received a Pre-Treatment and the Influence of Alkali Cleaning Fundamenta Procedure Preparation Procedure for the Pre-Treatment Compound

The separate pre-treatment compositions are prepared by combining the pre-treatment compound into a solvent and also additional compounds such as acid and mixing until uniform. The resulting mixture is the pre-treatment composition.

Hair pre-treatment procedure: Hair prepared as described above was treated with the pre-treatment composition described above, one gram of composition per one gram of hair. The composition was left on the hair between 1 and 5 min. The hair was then dried using a blow dryer with combing to result in dry hair.

Alkali Cleaning Fundamenta Procedure was performed exactly as described above on light blonde hair. The performance was then assessed using the Sebum Insult Test procedure.

In the following series of experiments, the pre-treatments and color compositions were made as per the formula tables and applied in sequence as described above. The curing conditions used were at room temperature for 36 h at room temperature and 50% relative humidity (ambient conditions) hours prior to performing the standard color remanence test.

1A 1B 1C 1D 1E 1F 1G 1H Pre-treatment Water Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Isopropanol 99 Acetic acid 0.08 0.08 0.08 0.08 0.08 PEI (50%) 1.00 Dynasylan MEMO² 5.00 Dynasylan GLYEO 5.00 Dynasylan OCTEO³ 5.00 Dynasylan MTMO⁴ 5.00 Dynasylan TRIAMO⁵ 5.00 1.00 Coloring Composition Belsil P1101 (50% in ethanol)⁶ 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 PERMUTEX XR-13-554⁷ 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Pigment red 122 Paste 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Phosphoric acid (85% in water) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Ammonia (25% in water) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Isopropanol Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Results Untreated hair color +++ +++ +++ +++ ++ +++ N/A N/A remanence Treated hair color +++ +++ +++ +++ ++ +++ N/A N/A remanence Sebum Insult color 0 ++ + + 0 ++ 0 ++ remanence Results with Alkali Clean Fundamenta Step Sebum Insult color +++ +++ ++ +++ ++ +++ 0 +++ remanence ²These acronyms stand for alkoxysilyl small molecules and are described in the specification. The Dynasylan materials are sold by Evonik Industries AG. ³octyltriethoxysilane ⁴3-mercaptopropyltrimethyoxysilane ⁵triaminoalkyltrimethoxysilane ⁶Belsil P1101 is an organosilicone with pendant carboxyl groups and is a copolymer of crotonic acid, C8-C23 isoalkyl vinyl ester, vinyl acetate and bis (vinyl) dimethicone. It is a commercial product sold by Wacker Chemical. ⁷A polycarbodiimide with in chain carbodiimides and alkyl links, sold by Stahl.

These experiments were performed to show the influence of pre-treatment on color remanence. The control experiment 1A showed already very strong color remanence on untreated hair and on treated hair. However, weak color remanence with a sebum insult test was observed. Therefore, the sebum insult color remanence test had been determines as the distinguishing test to choose the correct pre-treatment composition. The best performance was achieved with in experiments 1B, 1F and 1H with strong color remanence after sebum insult testing. These experiments contained polymers or silanes containing an amine group (1B and 1H) or a thiol group (1F). The experiments where the performance was only moderate or weak were experiments 1C, 1D, 1E, and 1G. In experiment 1C Dynasylan MEMO contained a methylacrylate reactive group, however the color remanence after sebum insult was only moderate. Experiment 1D contained Dynasylan GLYEO with an epoxy reactive group. However, the color remanence after sebum insult was also only moderate. The Dyansylan OCTEO in experiment 1E did not contain any reactive group but rather a long alkyl chain. The color remanence after sebum insult testing was weak. These results showed that the pre-treatment containing nucleophillic reactive groups (amines, thiols) work better than pre-treatments without reactive groups (octyl) or with electrophilic reactive groups (epoxy, methacrylate). Experiment 1G and 1H have shown that the amine containing condensation-curable silane Dynasilane TRIAMO needs particular conditions to be able to deposit on the surface and enhance the adhesion of the coating to the hair. If the Dynasylan TRIAMO was prepared by dissolving in water with a small amount of acetic acid present, as in experiment 1G, the effect on the color remanence was negative with weak remanence observed after the sebum insult test. However, if the Dynasylan TRIAMO was prepared in isopropanol without adding any acid, the effect on color remanence was very positive, with very strong remanence observed after sebum insult testing.

Example 2. Level of In-Situ Crosslinking Polymer System

The following experiments were performed to show the impact of the amount of in-situ crosslinking polymer system. The total level of organo-silicone polymer and the polycarbodiimide crosslinker is indicated in the table below. One set of light blonde tresses were used as received while another set were treated with the Alkali Clean Fundamenta technique prior to pre-treatment and coloration. The curing conditions were room temperature and ambient humidity for 36 hours after color application. Afterwards a Sebum insult color remanence test was performed.

2A 2B 2C 2D 2E Pre-treatment Water Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Acetic acid 0.08 0.08 0.08 0.08 0.08 Dynasylan MTMO 5.00 5.00 5.00 5.00 5.00 Coloring Composition Belsil P1101 (50% in 2.5 5.00 10.00  20.00  40.00  ethanol) PERMUTEX XR-13-554 0.50 1.00 2.00 4.00 8.00 Pigment red 122 Paste 10.00 10.00  10.00  10.00  10.00  Phosphoric acid (85% in 0.10 0.10 0.10 0.10 0.10 water) Ammonia (25% in water) 0.75 1.50 3.00 6.00 9.00 Isopropanol Qs to 100 Qs to 100 Qsto 100 Qs to 100 Qs to 100 Total Organo-silicone 1.75 3.50 7.00 14.00  28.00  Polymer + polycarbodiimide crosslinker actives Results Sebum Insult color 0 0   ++ ++ + remanence Results with Alkali Clean Fundamenta Step Sebum Insult color 0 +++ +++ +++ +++ remanence

The total solid concentration of organo-silicone polymer and polycarbodiimide crosslinker is included in the table and went from 1.75% in experiment 2A up to 28% in experiment 2E. The experiments show that on Sebum Insult tresses, the color remanence after sebum insult begins only after the solid level has reached 7.00%. This result is shown in experiment 2C with good color remanence. Once the solid level was high in experiment 2E at 28.00%, the performance started to drop off with only moderate color remanence when applied to Sebum Insult hair.

When the Alkali Clean Fundamenta technique was applied to the Sebum Insult hair before pre-treatment and coloration, the color remanence was very good already at a total solid level of 3.5% in experiment 2B. No remanence performance decrease appeared throughout the concentration range tested. Even experiment 2E at 28.00% solids level had very good color remanence after the Sebum Insult hair test with Fundamenta technique application.

Example 3. Pre-Treatment Compound Level

The following experiments were performed to show the impact of the pre-treatment compound level on performance. These were performed using a series of pre-treatment compositions followed by the same coloring composition. One set of light blonde tresses were used as received while another set were treated with the Alkali Clean Fundamenta technique prior to pre-treatment and coloration. The curing conditions were room temperature and ambient humidity for 36 hours after color application. Afterwards a mimic hair color remanence test was performed.

3A 3B 3C 3D 3E Pre-treatment Water Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Acetic acid 0.08 0.08 0.08 0.08 0.08 Dynasylan MTMO 0.10 1.00 2.50 5.00 10.00  Coloring Composition Belsil P1101 (50% in 10.00  10.00  10.00  10.00  10.00  ethanol) PERMUTEX XR-13-554 2.00 2.00 2.00 2.00 2.00 Pigment red 122 Paste 10.00  10.00  10.00  10.00  10.00  Phosphoric acid (85% in 0.10 0.10 0.10 0.10 0.10 water) Ammonia (25% in water) 3.00 3.00 3.00 3.00 3.00 Isopropanol Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Results Sebum Insult (Mimic hair) 0   0   + ++ +++ color remanence Results with Alkali Clean Fundamenta Step Sebum Insult (Mimic hair) ++ ++ +++ +++ +++ color remanence

The experiments show that the amount of pre-treatment is important. The amount of Dynasylan MTMO, a thiol based condensation-curable silane, was varied from 0.10% in experiment 3A up to 10% in experiment 3E. The Sebum insult testing showed that very strong color remanence could only be achieved at concentrations higher than 5% of Dynasilan MTMO with experiment 3E having a concentration of 10% and very strong performance. At 5% in experiment 3D the color remanence is strong and at 2.5% in experiment 3C the color remanence is medium, while in the experiments 3A and 3B with concentrations lower than 2.5% the color remanence is weak.

If the Alkali Cleaning Fundamenta step was performed on the hair tresses before the pre-treatment and color application, then the color remanence was significantly better already at low concentrations of Dynasilan MTMO. Already at 0.1% Dynasylan MTMO in experiment 3A the color remanence after Sebum Insult testing was strong. In experiment 3C with 2.50% Dynsylan MTMO the color remanence was already very strong and it remained such for the whole range of concentrations tested in subsequent experiments 3D an 3E with the highest concentration tested at 10%. Because the Sebum Insult hair tresses have the F layer (present on the original untreated hair tresses), this experiment shows that use of a technique to remove the F layer positively influences remanence.

Example 4. Impact of Praeparatur and Fundamenta Steps

The following experiments were performed to show the impact of using a Praeparatur and Fundamenta steps in conjunction with a Pre-treatment.

A full root hair simulation protocol was followed where the untreated light blond hair was first smeared with sebum to simulate the greasy hair at the root of the hair shaft near the scalp, i.e. mimic hair. Prior to any testing the light blonde hair tresses were first prepared to better simulate root hair found on a person. 0.1 g of sebum mimic (Hautfett nach BEY, sold by Wfk-Testgewebe GmbH) was applied to the individual hair tress weighing about 1 g described above. The tress was placed in an oven at 40° C. for 30 minutes.

Any steps that were required to color the hair tress with the required compositions were then performed. The colored coating was then left at 20° C. and ambient relative humidity for 36 hours. After these 36 hours the Standard Color Remanence test and the Sebum Insult Test (recoating with sebum after each shampooing) were performed.

4A 4B 4C 4D 4E 4F 4G 4H Praeparatur Step Shampoo None 2x 2x 2x None 2x 2x 2x Fundamental Step None None Alkali Plasma None None Alkali Plasma Clean Clean Pre-treatment Water none none none none Qs to 100 Qs to 100 Qs to 100 Qs to 100 Acetic acid none none none none 0.08 0.08 0.08 0.08 Dynasylan MTMO none none none none 5.00 5.00 5.00 5.00 Coloring Composition Belsil P1101 (50% in 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 ethanol) PERMUTEX XR-13-554 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Pigment red 122 Paste 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Phosphoric acid (85% in 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 water) Ammonia (25% in water) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Isopropanol Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Results Untreated Hair color 0 ++ +++ +++ 0 +++ +++ +++ remanence Treated Hair color 0 +++ ++ ++ ++ +++ +++ +++ remanence Sebum Insult (Mimic 0 0 + 0 0 + +++ +++ Hair) color remanence

Experiments 4A, 4B, 4C and 4D show the effect of Praeparatur and Fundamenta procedures without using any hair pre-treatment while experiments 4E, 4F, 4G and 4H show the effect of Praeparatur and Fundamenta procedures in conjunction with hair pre-treatment.

Experiment 4A is the control experiment. The color remanence was weak on untreated hair, on treated hair and also after a Sebum Insult test on the mimic hair. Experiment 4A in comparison with Experiment 1A shows the effect of dirt/sebum on the color remanence. The performance in Experiment 4A is much weaker than in Experiment 1A where the hair was not smeared with sebum before color application.

Experiment 4B shows the importance of cleaning the hair 2× with the Shampoo Praeparatur procedure. Color remanence was already improved in treated hair (very strong and on untreated hair (strong). However, the performance under further sebum insult was only weak.

Experiment 4C shows the impact of the Alkali Clean Fundamenta procedure in conjunction with the 2× Shampoo Praeparatur procedure. The performance was very strong on untreated hair, strong on treated hair and moderate after sebum insult.

Experiment 4D (no pretreatment composition) shows the impact of the Plasma Fundamenta procedure in conjunction with 2× Shampoo Praeparatur procedure. The performance was very strong on untreated hair, strong on treated hair and weak after sebum insult.

Experiment 4E shows how hair pre-treatment composition alone helps with color remanence on root mimic hair which has sebum deposits. The hair pre-treatment alone slightly improved the color remanence in comparison with Experiment 4A. Treated hair remanence was strong, but untreated hair remanence and sebum insult test color remanence was weak.

Experiment 4F shows the combination of 2× Shampoo Praeparatur and hair pre-treatment procedures. The color remanence after these two procedures were both used was very strong on untreated hair and on treated hair, however sebum insult performance was only moderate.

Experiment 4G shows the combination of 2× Shampoo Praeparatur, Alkali Clean Fundamenta and hair pre-treatment procedures. After all three procedures were performed before coloring the hair, the resulting color remanence was very strong on untreated hair, on treated hair and after sebum insult testing.

Experiment 4H shows the combination of 2× Shampoo Praeparatur, Plasma Fundamenta and hair pre-treatment procedures. After all three procedures were performed before coloring the hair, the resulting color remanence was very strong on untreated hair, on treated hair and after sebum insult testing.

Comparison of the results of Experiment 4E Sebum Insult with Experiments 4G and 4H (Sebum Insult) shows how priming and deep cleaning delivers significant remanence: 4E=weak; 4G, 4H=very strong. Comparison of the results of Experiments 4C and 4D (Sebum Insult) with 4G and 4H (Sebum Insult) shows the results of use of the pretreatment composition. While all four experiments involved priming and deep cleaning, without use of the pretreatment composition AND priming and deep cleaning, remanence declined significantly.

Statements of Embodiments of the Invention

The following statements of embodiments of the invention describe aspects, features and parameters of the methods, compositions, and treatments according to the invention. These statements provide further disclosure of these aspects, features and parameters and may serve as claims of the invention.

1. A method for producing a color coating on the surfaces of keratin fibers comprising

Preparing the keratin fibers to form primed and/or deep cleaned keratin fibers;

Applying to the primed keratin fibers a pretreatment composition to form pre-coated keratin fibers; and

Applying to the pre-coated keratin fibers a film forming composition to form a composite film of the film forming composition and pretreatment composition on the keratin fibers; and,

Converting the composite film to a color coating on the keratin fibers; wherein

The pretreatment composition comprises a compatible medium and at least one organosilicone small molecule with alkoxysilyl groups and/or organoamine groups or PEI, and preferably a small molecule;

The film forming composition comprises a compatible medium with one or more microparticle pigments and/or color bodies, a binder, and a linker wherein

the binder comprises an olefinic polymer, silicone polymer or olefinic-silicone block copolymer having at least 2 pendant and/or terminal carboxylic acid groups, binder being linear or branched, preferably linear; and

the linker comprises an alkylenyl, aromatic or alkylenyl aromatic polymer having multiple in chain segments of carbodiimide or a polymer of ester, urethane or urea monomeric residues having pendant and/or terminal alkylenyl single carbodiimide groups, the linker being linear or branched, preferably linear; and,

The primed and/or deep cleaned keratin fibers are prepared by removal of sebum and associated substances on the keratin fiber surfaces.

2. A method for producing a color coating on the surfaces of keratin fibers comprising

Applying to the keratin fibers a pretreatment composition to form pre-coated keratin fibers; and

Applying to the pre-coated keratin fibers a film forming composition to form a composite film of film forming composition and pretreatment composition on the keratin fibers; and,

Converting the composite film to the color coating on the keratin fibers; wherein

The pretreatment composition comprises a compatible medium and at least one organosilicone small molecule with pendant and/or terminal alkoxysilyl groups and/or organoamine groups or PEI, and preferably a small molecule;

The film forming composition comprises a compatible medium, one or more microparticle pigments and/or color bodies, a binder and a linker wherein

the binder comprises a olefinic polymer, silicone polymer or olefinic-silicone block copolymer having at least 2 pendant and/or terminal carboxylic acid groups, the binder being linear or branched, preferably linear; and

the linker comprises an alkylenyl, aromatic or alkylenyl aromatic polymer having multiple in chain segments of carbodiimide or a polymer of ester, urethane or urea monomeric residues having pendant and/or terminal alkylenyl single carbodiimide groups, the linker being linear or branched, preferably linear.

3. A method according to statement 1 or 2 wherein the keratin fibers are anagen hair, preferably hair on the scalp of a human. 4. A method according to any of the preceding statements wherein the binder comprises at least at least three carboxylic acid groups. 5. A method according to any of the preceding statements wherein the binder comprises an olefinic-silicone block polymer. 6. A method according to any of the preceding statements wherein the linker further comprises pendant and/or terminal alkoxysilyl groups. 7. A method according to any of the preceding statements wherein the binder comprises an olefinic polymer, a silicone polymer or an olefinic silicone block copolymer having along its backbone two or more pendant and/or terminal carboxylic acid groups, and at least one or more of a pendant group selected from an alkyl alkylenylcarboxylic ester group, an alkyl group, an alkylenyloxycarbonylalkyl group or a hydroxyalkyl group. 8. A method according to statement 7 wherein binder is an olefinic or olefinic silicone block copolymer and the pendant and/or terminal carboxylic acid groups are formed from one or more C3-C12 unsaturated mono or dicarboxylic acids, preferably one or more of (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, isoprenoic acid, pentenoic acid and/or pentadienoic acid. 9. A method according to any of the preceding statements wherein the composite film of pretreatment and film forming compositions is converted by drying and curing to form the color coating on the keratin fibers. 10. A method according to any of the preceding statements wherein the binder comprises a olefinic, silicone or organosilicone polymer of Formula I

MUE-(MU1)_(x)(MUX)_(y)-(MU2)_(z)-(MU3)_(a)(MU3X)_(b)-MUE   Formula I

wherein

MU1 comprises a hydrophobic olefinic monomeric unit comprising a linear C2-C10 alkene residue, a linear C4-C12 alkadiene residue and/or a C6-C10 aromatic/alkylaromatic vinyl residue,

MUX comprises an acidic olefinic monomeric unit comprising a linear C3-C10 alkenoic acid residue or a C4-C10 alkadienoic acid residue;

MU2 comprises a hydrophilic olefinic monomeric unit comprising a vinyl linear C2-C16 alkanoic ester residue, a C1-C14 linear alkyl or hydroxyalkyl linear C2-C14 alkenoic ester residue, a linear C2-C10 alkenoic amide residue or N—C1-C4 alkyl substituted version of the amide residue;

MU3 comprises a dimethylsiloxane residue;

MU3X comprises a monomethylsiloxane residue bound to an alkanoic acid of at least 4 carbons with one of the alkyl carbons of the alkanoic acid optionally having a hydroxy group; and

MUE comprises a single terminal monomeric unit of MU1, MU2, MU3, MUX or MU3 X;

each of the designators x, y, z, a and b independently designates the number of corresponding monomeric units forming the linear polymeric backbone, wherein each of x, z and a is zero or an integer of from 1 up to about 100,000 and y and b are each zero or an integer of 1 to 100;

when b is an integer, y may be zero or an integer and when b is zero, y is an integer;

the sum of x, y, z, a and b is an integer of from about 3 up to about 1 million, preferably up to about 300,000, more preferably up to about 250,000, most preferably up to about 200,000;

the multiple monomeric units of MU1, MU2 and MU3 are randomly distributed or form blocks in Formula I and the multiple carboxylic acid monomeric units MUX and MU3X are randomly distributed among MU1, MU2 and MU3 units; and,

the binder being linear or branched, preferably linear.

11. A method according to statement 10 wherein designators x and z are each at least 10, designator y is at least 3, designators a and b are both zero and terminal MUE is MUX. 12. A method according to statement 10 wherein each of designators x, z and a are 10 to 100, designator y is 1 to 50, designator b is zero, terminal MUE is MUX and the polymer is an organosilicone block copolymer. 13. A method according to statement 10 wherein designators x, y and z are zero, designator a is at least 20, preferably at least 40, designator b is 1 to 50 and terminal MUE is MU3 X. 14. A method according to any of statement 10 wherein each of designators x, z and a are 10 to 100, each of designators y and b independently is 1 to 50, terminal MUE is MUX or MU3X and the polymer is an organosilicone block copolymer. 15. A method according to any of statements 11-14 wherein the monomeric units are randomly distributed. 16. A method according to any of statements 11-14 wherein the monomeric units form block segments and when the binder is an organic polymer, the MU1 and MU2 units form blocks. 17. A method according to any of statements 10-16 wherein MU1 is butene, pentene, hexene, styrene, MUX is (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, fumaric acid, maleic acid, itaconic acid glutaconic acid, citraconic acid or mesaconic acid, MU2 is vinyl acetate, vinyl propanate, vinyl butanate, C1-C3 alkyl or hydroxyalkyl (meth)acrylate, C1-C3 alkyl or hydroxyalkyl crotonate, C1-C3 alkyl or hydroxyalkyl pentanoate, C1-C3 dialkyl or di-(hydroxyalkyl) fumarate, C1-C3 maleate or the corresponding primary amides or C1-C3 alkyl secondary amides and MU3X is MeSi(O)—R¹⁰—COOH wherein R¹⁰ is —(CH₂)_(n)—CHOH—(CH₂)₂—. 18. A method according to statement 17 wherein MU1 is hexene or styrene, MUX is (meth)acrylic acid or crotonic acid, MU2 is vinyl acetate, vinyl C8-C12 isoalkanoate, methyl, ethyl or isopropyl (meth)acrylate or the corresponding hydroxymethyl, hydroxyethyl or hydroxyisopropyl analogs, methyl, ethyl or isopropyl crotonate or the corresponding hydroxymethyl, hydroxyethyl or hydroxyisopropyl analogs and MU3X is -MeSi(O)—(CH₂)₃—CHOH—(CH₂)₂—COOH. 19. A method according to statement 18 wherein x zero, b is zero, a is at least 10, z is at least 10, y is 1 to 50, MUE is MUX and MU2 and MU3 form a block copolymer with MUX randomly distributed within MU2. 20. A method according to any of the preceding statements wherein the binder comprises at least monomeric units of alkyl (meth)acrylate and/or crotonate, and (meth)acrylic acid and/or crotonic acid; and the acid number of the polymer is from about 50 to about 600 preferably about 100 to about 400. 21. A method according to any of the preceding statements wherein the binder comprises at least an acid monomer as (meth)acrylic acid and/or crotonic acid at about 0.3% to about 75% by weight, a hydroxyethyl or hydroxypropyl (meth)acrylate and/or crotonate at about 0% to about 20% by weight and a hydrophobic monomer as methyl or ethyl (meth)acrylate and/or crotonate at about 5% to about 20% by weight, wherein all weights are relative to the total weight of the polymer. 22. A method according to any of the preceding statements wherein the linker comprises an organic polymer of Formula II, a polymer with in-chain carbodiimide groups or Formula X, a polymer with pendant single carbodiimide groups

Z-(L-N═C═N—)_(p)—Z   Formula II

(Poly)_(q)-(K)_(s)-(Poly)_(r)   Formula X

wherein;

for Formula II, p is an integer of at least 2; and L is an organic linker group comprising saturated aliphatic divalent radical, an aromatic divalent radical or an alkylaromatic divalent radical or a polymer or oligomeric divalent radical with repeating olefinic, carbonate, ester, ether, amide, imine, urethane or urea linkages;

For Formula X, each Poly is an organic polymer segment of an amide, imine, olefinic, caronate, ester, ether, urethan or urea monomeric residue and preferably the residue is an amide or urea/urethane monomeric residue is based upon a C3 to C6 alkane diamine and a C4-C10 alkane dicarboxylic acid or C4-C10 alkane diisocyanate, or an ester monomeric residue based upon a C3-C6 alkane diol and a C4-C10 alkane dicarboxylic acid and the designators q and r each being an integer of at least 2; K is a pendant carbodiimide group of Formula XI with s being an integer of at least 2

wherein R²⁰ is a C3 to C6 alkylenyl residue, R²¹ is a C3-C6 alkylenyl residue;

For Formulas II and XI Z is a non-reactive or reactive terminal group of the polycarbodiimide; and, the multiple K's are randomly distributed along the Poly backbone; L or Poly of the linker being linear or branched, preferably linear.

23. A method according to any of the preceding statements wherein the linker is Formula II, L is a saturated aliphatic divalent radical selected from linear or branched or cyclic alkylenyl of 2 to 20 carbons, an aromatic divalent radical selected from benzene or diphenyl, or an alkylaromatic divalent radical selected from p-dimethylenylphenyl or methylenyldiphenyl. 24. A method according to any of the preceding statements wherein the linker is Formula II, L is a saturated alkylenyl divalent radical of 2 to 6 carbons. 25. A method according to any of the preceding statements wherein the linker is Formula II, L is a residue of toluene, diphenylmethane, phenyl, dicyclohexyl methane, methyl-3,5,5,-trimethylcyclohexane, hexane, cyclohexane, norbornane. 26. A method according to any of the preceding statements wherein the linker is Formula II and L is dicyclohexylmethane, methyl-3,5,5-trimethylcyclohexane or hexane. 27. A method according to any of the preceding statements wherein the Z is a self-reacting C2-C6 alkylenylalkoxysilyl group. 28. A method according to any of the preceding statements wherein the linker is Formula II and Z is a nonreactive group comprising a saturated aliphatic monovalent radical selected from linear or branched or cyclic alkyl of 2 to 20 carbons, an aromatic monovalent radical selected from benzene or diphenyl, or an alkylaromatic monovalent radical selected from p-dimethylenylphenyl or methylenyldiphenyl. 29. A method according to any of the preceding statements wherein Z is butane or hexane. 30. A method according to any of the preceding statements wherein Z is hexane. 31. A method according to any of the preceding statements wherein the number of carbodiimide groups designated by p is from 2 to 100, preferably from 2 to 50, more preferably from 2 to 10, most preferably 2 to 5. 32. A method according to any of the preceding statements wherein the linker is Formula X, Poly is a polyamide or polyurea and the number of pendant carbodiimide K groups designated by s is from 2 to 50, preferably 2 to 10, more preferably 2 to 5. 33. A method according to any of the preceding statements wherein the linker is Formula X, Poly is a polyurethane and the number of pendant carbodiimide K groups designated by s is from 2 to 50, preferably 2 to 10, more preferably 2 to 5. 34. A method according to any of the preceding statements wherein the linker is Formula X, R²⁰ and R²¹ are each butylenyl or hexylenyl, and Z is butyl or hexyl. 35. A method according to any of the preceding statements wherein the binder of the film forming composition has a weight average molecular weight of about 0.5 KDa to about 500 KDa, preferably about 0.5 KDa to about 400 KDa, more preferably about 0.5 KDa to about 10 KDa, most preferably about 0.5 KDa to about 3 KDa to 5 KDa. 36. A method according to any of the preceding statements wherein the linker of the film forming composition has a weight average molecular weight of about 0.5 KDa to about 500 KDa, preferably about 0.5 KDa to about 400 KDa, more preferably about 0.5 KDa to about 10 KDa, most preferably about 0.5 KDa to about 3 KDa to 5 KDa. 37. A method according to any of the preceding statements wherein the compatible medium comprises a hydrocarbon, a silicone or an organic polar liquid, preferable an alcohol and more preferably a C2-C6 alkanol diol or triol, preferably isopropanol, propylene glycol or isobutanol. 38. A method according to any of the preceding statements wherein the medium is for application of the film forming composition and comprises an aqueous-organic medium and the water content is no more than about 10 wt %, preferably no more than about 5 wt %, more preferably no more than about 2 wt %, most preferably no more than about 1 wt % relative to the total weight of the medium. 39. A method according to any of the preceding statements wherein the medium is for separate storage of binder and linker of the film forming composition and is an anhydrous hydrocarbon, silicone or alcoholic medium. 40. A method according to any of the preceding statements wherein the concentration of the binder in the medium of the film forming composition comprises a weight percent range relative to the total weight of the film forming composition, of from about 2 wt % to about 8 wt %, preferably about 3 wt % to about 7 wt %, more preferably about 4 wt % to about 6 wt %. 41. A method according to any of the preceding statements wherein linker in the medium of the film forming composition comprises a weight percent range relative to the total weight of the film forming composition, of from about 2 wt % to about 8 wt %, preferably about 3 wt % to about 7 wt %, more preferably about 4 wt % to about 6 wt %. 42. A method according to any of the preceding statements wherein the pretreatment composition comprises at least one organosilicone small molecule comprising at least one pendant and/or terminal alkoxysilyl group and no or at least one pendant and/or terminal organoamine group. 43. A method according to any of the preceding statements wherein the organosilicone small molecule comprises pendant and/or terminal alkoxysilyl groups and pendant and/or terminal organoamine groups. 44. A method according to any of the preceding statements wherein the pretreatment composition comprises a mixture of at least an organosilicone small molecule with at least two alkoxysilyl groups and at least another organosilicone small molecule with an alkoxysilyl group and an organoamine group. 45. A method according to any of the preceding statements to any of statements 31-33 wherein the small molecule has an alkyl core to which is bonded the alkoxysilyl and organoamine groups. 46. A method according to any of the preceding statements to any of statements 31-34 wherein the small molecule has an organosilicone core to which is bonded the alkoxysilyl and organoamine groups. 47. A method according to any of the preceding statements wherein the small molecule of the pretreatment composition has Formula III

[(H₂N)—((CH₂)_(m)—NH)_(o)—(R¹⁴)_(n))]_(a)—[RO_(t)Me_(3-t)Si—O]_(b)—(—SiMe₂-O)_(p)—(—SiMeOR—O)_(q)—[(—SiMe_(2-r′)[(CH₂)_(m′)—NH₂]_(r)—O]_(s)-[A]_(c)-[(—SiMeMe_(2-v)-O]_(u)—SiMe_(3-t)OR_(t)   Formula III

wherein R may be methyl or ethyl;

R¹⁴ is a C1-C6 alkylenyl group;

Designators m and m′ may be an integer of 1 to 3; Designators o, n, b, r, s, c, u may be zero or 1; Designator a may be zero, 1 or 2; Designator v may be zero, 1 or 2 such that when a is 2, v is 2 and when a is 1, v is 1 and when a is zero, v is 1 or zero;

Designator t may be 1 to 3;

Designators p and q independently may be zero or an integer of 1 to 6; Designator t may be zero or an integer 1-3; Group A may be a divalent group including dithio, diazo, urethanyl, ureido, or C1-C6 alkylenyl connecting left and right sections of the small molecule, or Group A may be a terminal group including C1-C14 alkyl, C1X-C14X alkyl wherein X is N, S or O and X may be in-chain or terminal, C1-C6 alkoxy, C7-C14 arylalkyl, C6X-C14X heteroarylalkyl with X as N, S or O; C1-C6 alkylenyl(meth)acrylate or C1-C6 alkylureido. 48. A statement of a method according to any of the preceding statements wherein the small molecule comprises, and/or wherein the designators of Formula III of the preceding pretreatment statement are selected to provide, a trialkoxysilyl monoterminated compound having a two or three dimethylsiloxanyl silicon atoms and 1 to 3 aminoalkyl groups; a dipodal compound having trialkoxysilyl termini and an alkylenyl group connecting the termini; an aminoalkylalkoxysilyl compound having one, two or three silicon atoms; a silicone compound having alkoxysilyl groups and aminoalkyl groups; an alkylsiloxyl oligomer of from 2 to 6 silicons, having pendant aminoalkyl groups, having pendant alkyl-trialkoxysilane groups and trialkoxysilyl termini; an alkylsiloxyl oligomer of from 2 to 6 silicons having a terminal aminoalkyl group, a terminal trialkoxysilane group and pendant alkylalkoxysilane groups. 49. A statement of a method according to any of the preceding statements wherein the small molecule of the pretreatment composition is a dimethylsiloxane oligomer of 2 to 6 silicon atoms with multiple pendant and terminal groups of the formula —(CH₂)_(d′)—Si(OR)₃ and/or of the formula —(CH₂)_(d′)—NH₂ and/or of the formula —(CH₂)_(d)—NH—(CH₂)_(d)—NH₂ wherein d independently is an integer of 2 to 4 and d′ is zero or an integer of 1 to 3. 50. A statement of a method according to any of the preceding statements wherein the small molecule comprises at least one amine group and at least one triethoxysilyl group. 51. A statement of a method according to any of the preceding statements wherein the small molecule comprises a mixture of a first small molecule with at least one amine group and at least one triethoxy silyl group and a second small molecule with no amine groups and at least two triethoxysilyl groups. 52. A statement of a method according to any of the preceding statements wherein the small molecule of the pretreatment composition is aminopropyl triethoxysilane (APTES), trimethoxysilyl propyldiethylene triamine (SCA), trimethoxylsilyl propoxy (meth)acrylate ester (MEMO), propyl triethoxysilane (PTEO), ureidotrimethoxysilane (UREIDO), phenylsilane (PHS), tetraethoxysilane (TEOS), propylenyl or butenyl bis(trimethoxysilane) or C2-C6 mercaptoalkyl trimethoxy or triethoxysilane (MTS). 53. A statement of a method according to any of the preceding statements wherein the small molecule is APTES, SCA, PTEO, TEOS, MTS or any combination thereof. 54. A method according to any of the preceding statements further comprising a pretreatment composition of an amine polymer, preferably polyethyleneimine instead of, or in combination with a small molecule. 55. A method according to any of the preceding statements wherein the medium of the pretreatment composition comprises a hydrocarbon, a silicone, a polar organic liquid, preferably an alcohol and more preferably a C2-C6 alkanol organic medium, preferably isopropanol or isobutanol. 56. A method according to statement 55 wherein the alkanol is isopropanol. 57. A method according to any of the preceding statements wherein the pretreatment composition is applied to keratin fibers before applying the film forming composition or is applied simultaneously with application of the film forming composition to form a composite film on the keratin fibers. 58. A method according to any of the preceding statements to statement 46 wherein the composite film on keratin fibers is converted to a color coating by drying and/or curing. 59. A statement of a method according to any of the preceding statements further comprising priming and/or deep cleaning the keratin fibers by applying a Praeparatur and/or a Fundamenta technique to the fibers, wherein the Praeparatur and/or Fundamenta techniques comprise a Praeparatur step of treating the keratin fibers with a substantially non-conditioning or a non-conditioning surfactant composition to produce primed keratin fibers; and a Fundamenta step of deep cleaning the surfaces of the keratin fibers to form deep cleaned keratin fibers. 60. A statement of a method according to any of the preceding statements wherein the surfactant composition includes an anionic, nonionic, amphoteric or zwitterionic surfactant or a combination thereof at a concentration of from about 2 wt % to about 30 wt % relative to the total weight of the composition, preferably from about 10 wt % to about 25 wt % and optional inclusion of agents for adjustment of viscosity and ionicity and optional adjustment of the pH. 61. A statement of a method according to any of the preceding statements wherein the Prepaeratur step includes agitation of the keratin fibers by mechanical manipulation and/or by ultrasound vibration. 62. A statement of a method according to any of the preceding statements wherein the surfactant composition includes an anionic surfactant comprising a carboxylate, phosphate, sulfonate and/or sulfate head with a hydrophobic tail comprising a C8-C20 alkyl, a C8-C20 alkyl-polyethylene glycol or a C8-C20 alkyl-polypropylene glycol. 63. A statement of a method according to any of the preceding statements wherein the anionic surfactant is a sodium and/or potassium and/or ammonium salt of the carboxylate, phosphate, sulfonate and/or sulfate. 64. A statement of a method according to any of the preceding statements wherein the anionic surfactant is a sulfate. 65. A statement of a method according to any of the preceding statements wherein the anionic surfactant is a lauryl sulfate, laureth sulfate with a PEG-2 to PEG 30, preferably PEG 2-PEG 10, more preferably PEG 2 to PEG 5 or a laureth sulfate with a PPG-2 to PPG-30. 66. A statement of a method according to any of the preceding statements wherein the anionic surfactant is diluted with water to form an aqueous solution no more than about 30 wt % preferably nor more that about 10% to about 25 wt % of anionic surfactant relative to the total weight of the aqueous solution. 67. A statement of a method according to any of preceding statements further comprising an ionicity/viscosity builder modifier in the surfactant composition. 68. A statement of a method according to any of the preceding statements wherein the ionicity/viscosity builder modifier is an alkali metal salt of carbonate, phosphate, sulfate, nitrate or xylene sulfonate. 69. A statement of a method according to any of the statements wherein the pH is adjusted to be acidic, neutral or basic. 70. A statement of a method according to any of the preceding statements wherein the pH of the surfactant composition is adjusted to be basic with an alkali metal carbonate or bicarbonate. 71. A statement of a method according to any of the preceding statements wherein the agitation is accomplished by passing the keratin fibers through a fine tooth comb. 72. A statement of a method according to statement 71 wherein the teeth of the comb vibrate. 73. A statement of a method according to any of the preceding statements wherein the agitation is accomplished by passing the keratin fibers over and through an ultrasound device. 74. A statement of a method according to any of the preceding statements wherein the keratin fibers are passed through a fine tooth comb while agitating the fibers with an ultrasound device. 75. A statement of a method according to statement 74 wherein the ultrasound device operates at a frequency of at least 20 K Hertz. 76. A statement of a method according to any of the preceding statements wherein the priming and/or deep cleaning of the keratin fibers occurs before the pretreatment composition and/or film forming composition are applied to the keratin fibers. 77. A statement of a method according to any of the preceding statements wherein the keratin fibers comprise anagen hair on the scalp of a person and the hair is primed to remove dirt, grime and sebum. 78. A statement of a method according to any of the preceding statements wherein the Fundamenta technique treats the keratin fiber surfaces by deep cleaning the surface topography and removing fatty acids on the surfaces of the keratin fibers. 79. A statement of a method according to any of the preceding statements wherein the deep cleaning is accomplished by application of at least one of a cold plasma, a phase transfer tenside, an oxidizing compound or a combination thereof to the surfaces of the keratin fibers whereby the deep cleaning at least partially removes F layer fatty acid, sebum and optionally adjusts the topography at the surfaces of the keratin fibers. 1. A statement of a method according to any of the preceding statements wherein the cold plasma is a non-equilibrium atmospheric plasma of air or oxygen and/or nitrogen which has an effective temperature which approximates ambient temperature, and the phase transfer tenside is a multialkyl ammonium halide, preferably a C2-C20 alkyl trimethyl ammonium chloride or bromide, preferably cetyl or stearyl trimethylammonium bromide optionally with chlorine or bromine water and preferably alkali or thiol at basic pH. 80. A statement of a method according to any of the preceding statements wherein the Fundamenta technique adjusts the microsurface topography of the keratin fibers. 81. A statement of a method according to any of the preceding statements wherein the Fundamenta technique is applied along with the Praeparatur technique. 82. A statement of a method according to any of the preceding statements wherein the Fundamenta technique is applied to the keratin fibers without the Praeparatur technique. 83. A statement of a method according to any of the preceding statements wherein the keratin fibers are rinsed following either or both of the Praeparatur and Fundamenta techniques. 84. A statement of a method according to any of the preceding statements wherein the Fundamenta step includes rinsing the keratin fibers with a neutral to acidic medium optionally containing a surface preparation aid and drying the keratin fibers to form deep cleaned keratin fibers. 85. A statement of a method according to statement 85 wherein the surface preparation aid is at least an organic hydroxy mono or dicarboxylic acid or an alkali or nucleophilic compound. 86. A statement of a method according to statement 86 wherein the hydroxy mono or dicarboxylic acid is malic acid, glycolic acid, lactic acid, citric acid or a C5-C10 hydroxy alkanodioic acid and the alkali is carbonate, t-butoxide in t-butanol or is an alkyl or aromatic thiol. 87. A statement of a method according to any of the preceding statements comprising contacting the keratin fibers with a surfactant composition and mechanically distributing the surfactant composition throughout the fibers for at least 1 to 2 minutes, rinsing the surfactant composition from the fibers for at least 1 minute and optionally repeating the surfactant composition contact, distribution and rinsing to produce primed keratin fibers. 88. A statement of a method according to any of the preceding statements comprising contacting the primed keratin fibers with a cold plasma for at least 1 to 5 minutes followed by rinsing the keratin fibers to produce deep cleaned keratin fibers. 89. A statement of a method according to any of the preceding statements comprising contacting the keratin fibers or primed keratin fibers with a solution of fatty trimethyl C2-C20 alkyl ammonium chloride or bromide, preferably cetyl or stearyl trimethylammonium bromide and manipulating the solution throughout the fibers for a period of from 5 minutes to 30 minutes followed by rinsing to keratin fibers with a shampoo in acidic medium and/or in a basic medium with t-butanol and butoxide or aqueous carbonate to produce deep cleaned keratin fibers. 90. A statement of a method according to any of the preceding statements wherein the pretreatment composition is applied to the primed and/or deep cleaned keratin fibers by contacting the fibers with an absorbent material carrying the pretreatment composition to produce pre-coated keratin fibers having thereon the pretreatment composition on the surfaces of the keratin fibers. 91. A statement of a method according to statement 91 wherein the absorbent material is a sponge-like solid and sections of the keratin fibers are individually wiped with the absorbent material carrying the pretreatment composition so as to deposit the pretreatment composition on the surfaces of substantially all keratin fibers of each section. 92. A statement of a method according to statement 91 or 92 wherein the pre-coated keratin fibers are dried. 93. A statement of a method according to statement 93 wherein the drying is accomplished at a temperature above ambient so as to cure at least partially the small molecule of the precoated keratin fibers. 94. A statement of a method according to any of the preceding statements wherein the primed and/or deep cleaned pre-coated keratin fibers is contacted with an absorbent material carrying the film forming composition to produce a composite film of pretreatment composition and film forming composition on the keratin fibers. 95. A statement of a method according to any of the preceding statements wherein the absorbent material is a sponge-like solid and sections of the keratin fibers are individually wiped with the absorbent material carrying the film forming composition so as to deposit the film forming composition on the pre-coated keratin fibers to produce the composite film on the surfaces of substantially all keratin fibers of each section. 96. A statement of a method according to statement 95 wherein the composite film on the surfaces of the keratin fibers is dried. 97. A statement of a method according to statement 96 wherein the drying is accomplished at a temperature so as to cure at least partially the composite film and produce a color coating on the surfaces of the keratin fibers. 98. A statement of a method according to any of the previous statements wherein the pretreatment composition, the binder in compatible medium and linker in compatible medium are all maintained in separate containers until before use. 99. A statement of a method according to statement 98 wherein separate quantities of the binder and the linker each in a compatible medium are combined to form the film forming composition before application to keratin fibers. 100. A statement of a method according to any of the preceding statements wherein a coloration feature of the film forming composition comprises development of a series of premixes of pigments and dispersants and formation of the coloration feature by blending together a selection of premixes to produce a custom color mix of pigment selections and dispersants and combining the custom color mix with the film forming composition wherein the blending together of a selection of premixes is accomplished by correlating a spectrographic coloration analysis of the keratin fibers and applying a computer simulation to the coloration analysis and desired color to identify the selection of premixes for producing the desired color of the keratin fibers. 101. A method for producing a color coating on the surfaces of primed and/or deep cleaned keratin fibers comprising

Applying to the primed and/or deep cleaned keratin fibers a pretreatment composition to form pre-coated keratin fibers; and

Applying to the pre-coated keratin fibers a film forming composition to form a composite film of film forming composition and pretreatment composition on the keratin fibers; and,

Converting the film to the color coating on the keratin fibers;

wherein

the pretreatment composition comprises at least a C2-C4 alkanol medium and at least one organosilicone small molecule with at least one pendant and/or terminal alkoxysilyl group and at least one pendant and/or terminal organoamine group;

the film forming composition comprises at least a C2-C4 alkanol medium with one or more microparticle pigments and/or color bodies dispersed in the medium with a dispersant, a binder and a linker wherein;

the binder comprises a polymer having at least three pendant-terminal carboxylic acid groups wherein the polymer is linear and comprises

-   -   an olefinic polymer of one or more monomeric units of         (meth)acrylic ester, vinyl C8-C12 isoalkanoate ester, C3-C6         alkene, styrene and/or hydroxyalkyl (meth)acrylate; and one or         more monomeric acid units of (meth)acrylic acid maleic acid,         crotonic acid, fumaric acid and/or itaconic acid;     -   a silicone polymer of a backbone comprising dimethylsiloxane         units interspersed with methylsiloxanylalkylcarboxylic acid         units and terminated with dimethylsiloxane units; or     -   a block copolymer of blocks of the olefin polymer and the         silicone polymer; and,

the linker is linear and comprises multiple segments of a divalent radical coupled together with in-chain carbodiimide groups and terminated with C1-C3 alkylenyltrialkoxysilyl groups wherein the divalent radical is a hexylenyl radical, an isophoronyl radical, a p-dimethylenylphenyl radical or a methylenyl bis(cyclohexanyl) radical and the carbodiimide groups number from 3 to 100; and

The primed and/or deep cleaned keratin fibers are prepared by removal of sebum and associated substances and F layer fatty acids on the keratin fiber surfaces.

102. A method according to statement 101 wherein the organosilicone small molecule comprises an aminoalkyl trialkoxysilane. 103. A method according to statement 102 wherein the aminoalkyl is an aminoalkylenylaminoalkylenykaminoalkyenyl)_(n)-group wherein each alkylenyl is a C2-C4 alkylenyl group and n is zero or one; and alkoxy is methoxy or alkoxy. 104. A method according to statement 103 wherein the organosilicone small molecule is aminoethylenylaminoethylenylaminopropylenyltrimethoxysilane. 105. A method according to statement 101 wherein the pretreatment composition further comprises an amine polymer, preferably polyethyleneimine instead of, or in combination with a small molecule. 106. A method according to any of statements 101-105 wherein the binder comprises the linear olefin-silicone block copolymer of bis-vinyl dimethicone, vinyl C8-C12 isoalkanoate ester, and an olefinic acid monomer selected from crotonic acid, maleic acid and/or (meth)acrylic acid units wherein the binder has at least 3 to 6 carboxylic acid groups per molecule and a weight average molecular weight of from about 1 KDa to about 10 KDa and the linker comprises a linear carbodiimide polymer of from about 5 to about 25 carbodiimide groups interconnected with divalent isophoronyl radicals, phenyl-1,4-dimethylenyl radicals, methylenyl bis(cyclohexanyl) radicals and terminated with C3-C6 alkylenyl triethoxysilyl groups wherein the linker has a weight average molecule weight of from about 0.5 KDa to about 5 KDa. 107. A method according to any of statements 101-105 further comprising priming the keratin fibers before application of the pretreatment and film forming compositions wherein the keratin fibers are anagen hair; the priming comprises contacting the keratin fibers with a substantially non-conditioning or a non-conditioning anionic surfactant medium optionally containing one or more agents for adjustment of viscosity and ionicity and adjustment to a basic pH, and the contacting includes mechanical manipulation of the keratin fibers covered with anionic surfactant medium for at least 30 seconds followed by rinsing the anionic surfactant medium from the keratin fibers and optionally repeating the anionic surfactant medium contacting and rinsing steps to produce primed keratin fibers. 108. A method according to statement 107 further comprising deep cleaning the primed keratin fibers by contacting them with at least one of a cold plasma, a phase transfer tenside, an oxidizing compound or a combination thereof to form primed, deep cleaned keratin fibers wherein the cold plasma is a jetted stream of ionized air or helium at approximate ambient temperature wherein the jetted stream is played over the keratin fibers from proximal to distal ends; the phase transfer tenside is a C2-C20 multi-alkyl ammonium halide preferably a trimethyl C2-C20 fatty alkyl ammonium halide, more preferably a trimethyl cetyl or stearyl ammonium chloride or bromide in alkali at basic pH optionally with chlorine or bromine water; and the oxidizing compound is ozone, hydrogen peroxide benzoyl peroxide or alkali metal persulfate or alkali metal hypochlorite wherein the phase transfer tenside or the oxidizing compound is mechanically manipulated throughout the keratin fibers. 109. A method according to any of statements 107-108 wherein the keratin fibers are contacted by dividing the keratin fibers into sections and contacting the keratin fibers from distal ends to proximal ends. 110. A method according to any of statements 107-109 further comprising rinsing the keratin fibers with a neutral to acidic medium and/or basic medium optionally containing a surface preparation aid and drying the keratin fibers to form primed, deep cleaned keratin fibers. 111. A method according to statement 110 wherein the surface preparation aid is at least an organic hydroxy mono or dicarboxylic acid, preferably malic acid, glycolic acid, lactic acid, or a C5-C10 hydroxy alkanodioic acid or a base as at least a carbonate, t-butoxide in t-butanol or a nucleophilic compound including an organic amine or thiol. 112. A method according to any of statements 101-111 wherein the keratin fibers are anagenic hair, hair on the scalp of a human or shorn hair formed into swatches and coated with natural or synthetic sebum.

Composition Statements

B1 A keratin fiber coloring composition comprising

A pretreatment composition comprising a compatible medium and at least one organosilicone small molecule with pendant and/or terminal alkoxysilyl groups and/or organoamine groups;

A film forming composition comprising a compatible medium, one or more microparticle pigments and/or color bodies, a binder and a linker wherein the binder is linear and/or branched, preferably linear and comprises a olefinic polymer, a silicone polymer or an olefinic-silicone block polymer having at least 2 pendant and/or terminal carboxylic acid groups and the linker is linear or branched, preferably linear and comprises multiple segments of a saturated aliphatic divalent radical, an aromatic divalent radical or an alkylaromatic divalent radical coupled together with in-chain carbodiimide groups and terminated with alkoxysilyl groups or a polymer of ester, urethane or urea monomeric residues having pendant and/or terminal alkylenyl single carbodiimide groups; and, wherein the pretreatment composition is adapted to form a layer of a cured small molecule network on the keratin fibers thereby providing precoated hair, and the binder and linker are maintained separately until immediately before use and are combined together to form a mixture for application of the mixture to the precoated keratin fibers to form a colored coating on the keratin fibers.

B2 A keratin fiber coloring composition according to any of the preceding composition statements wherein the binder comprises at least at least three carboxylic acid groups. B3 A keratin fiber coloring composition according to any of the preceding composition statements wherein the binder comprises an olefinic-silicone block polymer. B4 A keratin fiber coloring composition according to any of the preceding statements wherein the linker comprises pendant and/or terminal alkoxysilyl groups. B5 A keratin fiber coloring composition according to any of the preceding composition statements wherein the binder comprises an olefinic polymer, a silicone polymer or an olefinic silicone block copolymer having along its backbone one or more pendant alkyl alkylenylcarboxylic ester groups, one or more pendant alkylenyloxycarbonylalkyl groups, one or more pendant hydroxyalkyl groups and/or pendant alkyl groups and two or more pendant and/or terminal carboxylic acid groups. B6 A keratin fiber coloring composition according to any of the preceding composition statements wherein binder is an olefinic or olefinic-silicone block copolymer and the pendant and/or terminal carboxylic acid groups are formed from one or more C3-C12 unsaturated mono or dicarboxylic acids, preferably the C3-C12 unsaturated mono or dicarboxylic acid is one or more of (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, isoprenoic acid, pentenoic acid and/or pentadienoic acid. B7 A keratin fiber coloring composition according to any of the preceding composition statements wherein the binder comprises a linear or branched, preferably linear organic or organosilicone polymer of Formula I

MUE-(MU1)_(x)(MUX)_(y)-(MU2)_(z)-(MU3)_(a)(MU3X)_(b)-MUE   Formula I

wherein

MU1 comprises a hydrophobic olefinic monomeric unit comprising a C2-C10 alkene residue, a C4-C12 alkadiene residue and/or a C6-C10 aromatic/alkylaromatic vinyl residue,

MUX comprises an acidic olefinic monomeric unit comprising a C3-C10 alkenoic acid residue or a C4-C10 alkadienoic acid residue;

MU2 comprises a hydrophilic olefinic monomeric unit comprising a vinyl C2-C16 alkanoic ester residue, a C1-C14 alkyl or hydroxyalkyl linear C2-C14 alkenoic ester residue, a C2-C10 alkenoic amide residue or N—C1-C4 alkyl substituted version of the amide residue;

MU3 comprises a dimethylsiloxane residue;

MU3X comprises a monomethylsiloxane residue bound to an alkanoic acid of at least 4 carbons with one of the alkyl carbons of the alkanoic acid optionally having a hydroxy group; and

MUE comprises a single terminal monomeric unit of MU1, MU2, MU3, MUX or MU3 X;

each of the designators x, y, z, a and b independently designates the number of monomeric units forming the corresponding linear or branched polymeric backbone, wherein each of x, z and a is zero an integer of from 1 up to about 100,000 and y and b are each zero or an integer of 1 to 100;

when b is an integer, y may be zero or an integer and when b is zero, y is an integer;

the sum of x, y, z, a and b is an integer of from about 3 up to about 1 million, preferably up to about 300,000, more preferably up to about 250,000, most preferably up to about 200,000; and

the multiple monomeric units of MU1, MU2 and MU3 are randomly distributed or form blocks in Formula I and the multiple carboxylic acid monomeric units MUX and MU3X are randomly distributed among MU1, MU2 and MU3 units.

B8 A keratin fiber coloring composition according to statement B7 wherein designators x and z are each at least 10, designator y is at least 3, designators a and b are both zero and MUE is MUX. B9 A keratin fiber coloring composition according to statement B7 wherein each of designators x, z and a are 10 to 100, designator y is 1 to 50, designator b is zero, MUE is MUX and the polymer is an organosilicone block copolymer. B10 A keratin fiber coloring composition according to statement B7 wherein designators x, y and z are zero, designator a is at least 20, preferably at least 40, designator b is 1 to 50 and MUE is MU3X. B11 A keratin fiber coloring composition according to any of statement B7 wherein each of designators x, z and a are 10 to 100, each of designators y and b independently is 1 to 50, MUE is MUX or MU3X and the polymer is an organosilicone block copolymer. B12 A keratin fiber coloring composition according to any of statements B7-B11 wherein the monomeric units are randomly distributed. B13 A keratin fiber coloring composition according to any of statements B7-B11 wherein the monomeric units form block segments and when the binder is an organic polymer, the MU1 and MU2 units form blocks. B14 A keratin fiber coloring composition according to any of statements B7-B13 wherein MU1 is butene, pentene, hexene, styrene, MUX is (meth)acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, fumaric acid, maleic acid, itaconic acid glutaconic acid, citraconic acid or mesaconic acid, MU2 is vinyl acetate, vinyl propanate, vinyl butanate, C1-C3 alkyl or hydroxyalkyl (meth)acrylate, C1-C3 alkyl or hydroxyalkyl crotonate, C1-C3 alkyl or hydroxyalkyl pentanoate, C1-C3 dialkyl or di-(hydroxyalkyl) fumarate, C1-C3 maleate or the corresponding primary amides or C1-C3 alkyl secondary amides and MU3X is MeSi(O)—R¹⁰—COOH wherein R′° is —(CH₂)_(n)—CHOH—(CH₂)₂—. B15 A keratin fiber coloring composition according to statement B14 wherein MU1 is hexene or styrene, MUX is (meth)acrylic acid or crotonic acid, MU2 is vinyl acetate, vinyl C8-C12 isoalkanoate, methyl, ethyl or isopropyl (meth)acrylate or the corresponding hydroxymethyl, hydroxyethyl or hydroxyisopropyl analogs, methyl, ethyl or isopropyl crotonate or the corresponding hydroxymethyl, hydroxyethyl or hydroxyisopropyl analogs and MU3X is -MeSi(O)—(CH₂)₃—CHOH—(CH₂)₂—COOH. B16 A keratin fiber coloring composition according to statement B15 wherein x zero, b is zero, a is at least 10, z is at least 10, y is 1 to 50, MUE is MUX and MU2 and MU3 form a block copolymer with MUX randomly distributed within MU2 and MU3. B17 A keratin fiber coloring composition according to any of the preceding composition statements wherein the binder comprises at least monomeric units of alkyl (meth)acrylate and/or crotonate, and (meth)acrylic acid and/or crotonic acid; and the acid number of the polymer is from about 50 to about 600 preferably about 100 to about 400. B18 A keratin fiber coloring composition according to any of the preceding statements wherein the binder comprises at least an acid monomer as (meth)acrylic acid and/or crotonic acid at about 0.3% to about 75% by weight, a hydroxyethyl or hydroxypropyl (meth)acrylate and/or crotonate at about 0% to about 20% by weight, a hydrophobic monomer as methyl or ethyl (meth)acrylate and/or crotonate at about 5% to about 20% by weight, and an olefin monomer at zero percent up to about 10% by weight, wherein all weights are relative to the total weight of the polymer. B19 A method according to any of the preceding statements wherein the linker comprises a linear or branched, preferably linear organic polymer of Formula II, a polymer with in-chain carbodiimide groups or Formula X, a polymer with pendant single carbodiimide groups

Z-(L-N═C═N—)_(p)—Z   Formula II

(Poly)_(q)-(K)_(s)-(Poly)_(r)   Formula X

wherein;

for Formula II, p is an integer of at least 2; and L is an organic linker group comprising saturated aliphatic divalent radical, an aromatic divalent radical or an alkylaromatic divalent radical or a polymer or oligomeric divalent radical with repeating olefinic, carbonate, ester, ether, amide, urethane or urea linkages;

For Formula X, each Poly is an organic polymer segment of amide, urea urethane ester, carbonate or olefinic monomeric residues, preferably amide or urea/urethane monomeric residues based upon a C3 to C6 alkane diamine and a C4-C10 alkane dicarboxylic acid or C4-C10 alkane diisocyanate, or an ester monomeric residue based upon a C3-C6 alkane diol and a C4-C10 alkane dicarboxylic acid and the designators q and r each being an integer of at least 2; K is a pendant carbodiimide group of Formula XI with s being an integer of at least 2

wherein R²⁰ is a C3 to C6 alkylenyl residue, R²¹ is a C3-C6 alkylenyl residue;

For Formulas II and XI Z is a non-reactive or reactive terminal group of the polycarbodiimide; and, the multiple K's are randomly distributed along the Poly backbone.

B20 A method according to any of the preceding statements wherein the linker is Formula II, L is a saturated aliphatic divalent radical selected from linear or branched or cyclic alkylenyl of 2 to 20 carbons, an aromatic divalent radical selected from benzene or diphenyl, or an alkylaromatic divalent radical selected from p-dimethylenylphenyl or methylenyldiphenyl. B21 A method according to any of the preceding statements wherein the linker is Formula II, L is a saturated alkylenyl divalent radical of 2 to 6 carbons. B22 A method according to any of the preceding statements wherein the linker is Formula II, L is a residue of toluene, diphenylmethane, phenyl, dicyclohexyl methane, methyl-3,5,5,-trimethylcyclohexane, hexane, cyclohexane, norbornane. B23 A method according to any of the preceding statements wherein the linker is Formula II and L is dicyclohexylmethane, methyl-3,5,5-trimethylcyclohexane or hexane. B24 A method according to any of the preceding statements wherein the Z is a self-reacting C2-C6 alkylenylalkoxysilyl group. B25 A method according to any of the preceding statements wherein the linker is Formula II and Z is a nonreactive group comprising a saturated aliphatic monovalent radical selected from linear or branched or cyclic alkyl of 2 to 20 carbons, an aromatic monovalent radical selected from benzene or diphenyl, or an alkylaromatic monovalent radical selected from p-dimethylenylphenyl or methylenyldiphenyl. B26 A method according to any of the preceding statements wherein Z is butane or hexane. B27 A method according to any of the preceding linker statements wherein Z is hexane. B28 A method according to any of the preceding statements wherein the number of carbodiimide groups designated by p is from 2 to 100, preferably from 2 to 50, more preferably from 2 to 10, most preferably 2 to 5. B29 A method according to any of the preceding statements wherein the linker is Formula X, Poly is a polyamide or polyurea and the number of pendant carbodiimide K groups designated by s is from 2 to 50, preferably 2 to 10, more preferably 2 to 5. B30 A method according to any of the preceding statements wherein the linker is Formula X, Poly is a polyurethane and the number of pendant carbodiimide K groups designated by s is from 2 to 50, preferably 2 to 10, more preferably 2 to 5. B31 A method according to any of the preceding statements wherein the linker is Formula X, R²⁰ and R²¹ are each butylenyl or hexylenyl, and Z is butyl or hexyl. B32 A keratin fiber coloring composition according to any of the preceding statements wherein the binder of the film forming composition has a weight average molecular weight of about 0.5 KDa to about 500 KDa, preferably about 0.5 KDa to about 400 KDa, more preferably about 0.5 KDa to about 10 KDa, most preferably about 0.5 KDa to about 3 KDa to 5 KDa. B33 A keratin fiber coloring composition according to any of the preceding statements wherein the linker of the film forming composition has a weight average molecular weight of about 0.5 KDa to about 500 KDa, preferably about 0.5 KDa to about 400 KDa, more preferably about 0.5 KDa to about 10 KDa, most preferably about 0.5 KDa to about 3 KDa to 5 KDa. B34 A keratin fiber coloring composition according to any of the preceding statements wherein the compatible medium is an organic medium, preferably is a C2-C6 alkanol, preferably isopropanol or isobutanol. B35 A keratin fiber coloring composition according to any of the preceding statements wherein the medium for the pretreatment composition and the film forming composition immediately prior to use is an aqueous-organic medium and the water content is no more than about 10 wt %, preferably no more than about 5 wt %, more preferably no more than about 2 wt %, most preferably no more than about 1 wt % relative to the total weight of the medium. B36 A keratin fiber coloring composition according to any of the preceding statements wherein the concentration of the binder in the medium of the film forming composition comprises a weight percent range relative to the total weight of the film forming composition, of from about 2 wt % to about 8 wt %, preferably about 3 wt % to about 7 wt %, more preferably about 4 wt % to about 6 wt %. B37 A keratin fiber coloring composition according to any of the preceding statements wherein linker in the medium of the film forming composition comprises a weight percent range relative to the total weight of the film forming composition, of from about 2 wt % to about 8 wt %, preferably about 3 wt % to about 7 wt %, more preferably about 4 wt % to about 6 wt %. B38 A keratin fiber coloring composition according to any of the preceding statements wherein the pretreatment composition comprises at least one organosilicone small molecule comprising at least one pendant and/or terminal alkoxysilyl group and no or at least one pendant and/or terminal organoamine group. B39 A keratin fiber coloring composition according to any of the preceding statements wherein the organosilicone small molecule comprises pendant and/or terminal alkoxysilyl groups and pendant and/or terminal organoamine groups. B40 A keratin fiber coloring composition according to any of the preceding statements wherein the pretreatment composition comprises a mixture of at least an organosilicone small molecule with at least two alkoxysilyl groups and at least an organosilicone small molecule with an alkoxysilyl group and an organoamine group. B41 A keratin fiber coloring composition according to any of the preceding statements wherein the small molecule has an alkyl core to which is bonded the alkoxysilyl and organoamine groups. B42 A keratin fiber coloring composition according to any of the preceding statements wherein the small molecule has an organosilicone core to which is bonded the alkoxysilyl and organoamine groups. B43 A keratin fiber coloring composition according to any of the preceding statements wherein the small molecule of the pretreatment composition has Formula III

[(H₂N)—((CH₂)_(m)—NH)_(o)—(R¹⁴)_(n))]_(a)—[RO_(t)Me_(3-t)Si—O]_(b)—(—SiMe₂-O)_(p)—(—SiMeOR—O)_(q)—[(—SiMe_(2-r′)[(CH₂)_(m′)—NH₂]_(r)—O]_(s)-[A]_(c)-[(—SiMeMe_(2-v)-O]_(u)—SiMe_(3-t)OR_(t)   Formula III

wherein

R may be methyl or ethyl;

-   -   R¹⁴ is a C1-C6 alkylenyl group;

Designators m and m′ may be an integer of 1 to 3;

Designators o, n, b, r, s, c, u may be zero or 1;

Designator a may be zero, 1 or 2;

Designator v may be zero, 1 or 2 such that when a is 2, v is 2 and when a is 1, v is 1 and when a is zero, v is 1 or zero;

Designator t may be 1 to 3;

Designators p and q independently may be zero or an integer of 1 to 6;

Designator t may be zero or an integer 1-3;

Group A may be a divalent group including dithio, diazo, urethanyl, ureido, or C1-C6 alkylenyl connecting left and right sections of the small molecule, or Group A may be a terminal group including C1-C14 alkyl, C1X-C14X alkyl wherein X is N, S or O and X may be in-chain or terminal, C1-C6 alkoxy, C7-C14 arylalkyl, C6X-C14X heteroarylalkyl with X as N, S or O; C1-C6 alkylenyl(meth)acrylate or C1-C6 alkylureido.

B44 A keratin fiber coloring composition according to any of the preceding statements wherein the designators of Formula III are selected to provide a trialkoxysilyl monoterminated compound having a two or three dimethylsiloxanyl silicon atoms and 1 to 3 aminoalkyl groups; a dipodal compound having trialkoxysilyl termini and an alkylenyl group connecting the termini; aminoalkylalkoxysilyl compound having one, two or three silicon atoms; a silicone compound having alkoxysilyl groups and aminoalkyl groups; an alkylsiloxyl oligomer of from 2 to 6 silicons, having pendant aminoalkyl groups, having pendant alkyl-trialkoxysilane groups and trialkoxysilane termini; an alkylsiloxyl oligomer of from 2 to 6 silicons having a terminal aminoalkyl group, a terminal trialkoxysilane group and pendant alkylalkoxysilane groups. B45 A keratin fiber coloring composition according to any of the preceding statements wherein the small molecule of the pretreatment composition is a dimethylsiloxane oligomer of 2 to 10 silicon atoms with multiple pendant and terminal groups of the formula —O—(CH₂)_(d)—Si(OR)₃ and/or of the formula —O—(CH₂)_(d)—NH₂ and/or of the formula —O—(CH₂)_(d)—NH—(CH₂)_(d)—NH₂ wherein each d independently is an integer of 4 to 8. B46 A keratin fiber coloring composition according to any of the preceding statements wherein the small molecule comprises at least one amine group and at least one triethoxysilyl group. B47 A keratin fiber coloring composition according to any of the preceding statements wherein the small molecule comprises a mixture of a first small molecule with at least one amine group and at least one triethoxy silyl group and a second small molecule with no amine groups and at least two triethoxysilyl groups. B48 A keratin fiber coloring composition according to any of the preceding statements wherein the small molecule of the pretreatment composition is aminopropyl triethoxysilane (APTES), trimethoxysilyl propyldiethylene triamine (SCA), trimethoxylsilyl propoxy (meth)acrylate ester (MEMO), propyl triethoxysilane (PTEO), ureidotrimethoxysilane (UREIDO), phenylsilane (PHS), tetraethoxysilane (TEOS), propylenyl or butenyl bis(trimethoxysilane), mercaptopropyltrimethoxyor triethoxysilane (MPTS) hydroxydimethylsilyldimethylsiloxymethyl siloxy(propylaminoethylamine), dimethylhydroxysiloxane (silamine), said silamine in which the hydroxy groups are converted to methoxy groups, or any combination of said small molecules. B49 A keratin fiber coloring composition according to any of the preceding statements wherein the small molecule is APTES, SCA, PTEO, TEOS, MPTS or any combination thereof. B50 A keratin fiber coloring composition according to any of the preceding statements further comprising a pretreatment composition of an amine polymer, preferably polyethyleneimine instead of or in combination with a small molecule. B51 A keratin fiber coloring composition according to any of the preceding statements wherein the pretreatment composition comprises a C2-C6 alkanol organic medium, preferably isopropanol or isobutanol. B52 A keratin fiber coloring composition according to any of the preceding statements wherein the alkanol medium is isopropanol. B53 A keratin fiber coloring composition comprising a pretreatment composition and a film forming composition for application to primed and/or deep cleaned keratin fibers, wherein the pretreatment composition is adapted for forming a layer of a small molecule network on the keratin fibers thereby providing precoated hair, and the film forming composition comprises a binder and linker which are maintained separately until immediately before use and are combined together to form a mixture for application to the precoated keratin fibers to form a colored coating on the keratin fibers; and wherein,

The pretreatment composition comprises at least a C2-C4 alkanol medium and at least one organosilicone small molecule with at least one pendant and/or terminal alkoxysilyl group and at least one pendant and/or terminal organoamine group;

The film forming composition comprises at least a C2-C4 alkanol medium with one or more microparticle pigments and/or color bodies dispersed in the medium with a dispersant, a binder and a linker wherein;

-   -   The binder is linear and comprises a polymer having at least         three pendant-terminal carboxylic acid groups wherein the         polymer is linear and comprises         -   an olefinic polymer of one or more monomeric units of             (meth)acrylic ester, vinyl C8-C12 isoalkanoate ester, C3-C6             alkene, styrene and/or hydroxyalkyl (meth)acrylate; and one             or more monomeric acid units of (meth)acrylic acid maleic             acid, crotonic acid, fumaric acid and/or itaconic acid;         -   a silicone polymer of a backbone comprising dimethylsiloxane             units interspersed with methylsiloxanylalkylcarboxylic acid             units and terminated with dimethylsiloxane units; or         -   a block copolymer of blocks of the olefin polymer and the             silicone polymer; and,

the linker is linear and comprises multiple segments of a divalent radical coupled together with in-chain carbodiimide groups and terminated with C1-C3 alkylenyltrialkoxysilyl groups wherein the divalent radical is a hexylenyl radical, an isophoronyl radical, a p-dimethylenylphenyl radical or a methylenyl bis(cyclohexanyl) radical and the carbodiimide groups number from 3 to 100.

B54 A keratin fiber coloring composition according to statement B53 wherein the organosilicone small molecule comprises an aminoalkyl trialkoxysilane. B55 A keratin fiber coloring composition according to statement B54 wherein the aminoalkyl is an aminoalkylenylaminoalkylenyl-(aminoalkyenyl)_(n)-group wherein each alkylenyl is a C2-C4 alkylenyl group and n is zero or one; and alkoxy is methoxy or alkoxy. B56 A keratin fiber coloring composition according to statement B55 wherein the organosilicone small molecule is aminoethylenylaminoethylenylaminopropylenyltrimethoxysilane. B57 A keratin fiber coloring composition according to statement B53 wherein the pretreatment composition further comprises an amine polymer, preferably polyethyleneimine instead of or in combination with a small molecule. B58 A keratin fiber coloring composition according to any of statements 46-50 wherein the binder comprises the linear olefin-silicone block copolymer of bis-vinyl dimethicone, vinyl C8-C12 isoalkanoate ester, and an olefinic acid monomer selected from crotonic acid, maleic acid and/or (meth)acrylic acid units wherein the binder has a weight average molecular weight of from about 1 KDa to about 10 KDa and the linker comprises a linear carbodiimide polymer of from about 5 to about 25 carbodiimide groups interconnected with divalent isophoronyl radicals, phenyl-1,4-dimethylenyl radicals, methylenyl bis(cyclohexanyl) radicals and terminated with C3-C6 alkylenyl triethoxysilyl groups wherein the linker has a weight average molecule weight of from about 0.5 KDa to about 5 KDa.

Kit Statements

B59 A kit according to any of the preceding B1-B58 statements wherein the pretreatment composition, the binder and the linker are maintained in separate containers until use.

Dispersant

Statement 1, dispersant. The film forming composition of any of the preceding statements of keratin color compositions and the film forming composition of any of the preceding statements of methods, wherein the film forming composition further comprises: a dispersion of pigment particles and/or color bodies and pigment dispersant. Statement 2, dispersant. The film forming composition of Statement 1 wherein the dispersion of pigment particles and/or color bodies and pigment dispersant is compatible with the film forming composition. Statement 3, dispersant. The film forming composition of Statement 1 or 2 wherein the dispersion of pigment particles and/or color bodies and pigment dispersant is not compatible with the pretreatment composition. Statement 4, dispersant. The film forming composition of any Statement 1 or 2 wherein the dispersion of pigment particles and/or color bodies and pigment dispersant is compatible with the pretreatment composition. Statement 5 dispersant. The film forming composition of any of Statements 1˜4 wherein the pigment particles and/or color bodies are coated with polyvinyl fluoride.

Additives

Statement 1 additive. The film forming composition of any of the preceding statements of keratin coloring composition, and the film forming composition of any of the preceding statements of methods, wherein the film forming composition further comprises an additive comprising one or more of a microfibril having a fiber length between 1 nanometer and 10 micrometers; a non-chromatic filler material with a particle size between 2 nm and 500 nm; a polyolefin as macromolecular strands or nanoparticles wherein the nanoparticles are selected from the group consisting of smectites, kaolins, illites, chlorites, attapulgites and mixtures or inorganic metal oxides selected from the group consisting of silica, titanium oxide, zirconium oxide, aluminum oxide, magnesium oxide, boehmite alumina, hydrotalcite; a carbon nanotube; nanofiller of graphite oxide mixed polymer; a graphene additive; one or more UV filters; one or more radical scavengers; one or more triplet formation inhibitors; a metal compound which can absorb or reflect UV light, wherein the metal compounds are selected from chromium, titanium, zinc, nickel, manganese, iron, niobium, silver, gold, aluminum, hafnium, tantalum; polyvinylidene fluoride for UV protection and chemical resistance.

Topcoat

Statement T1, topcoat. A post-color coating composition comprising a medium and a topcoat composite. Statement T2, topcoat. The post-color coating composition of statement T1 wherein the topcoat composite is one or more of a UV filter, a visible light filter, a radical scavenger, a triplet formation inhibitor, a water repellant, a hair spray formulation for holding a hair style or any combination thereof. Statement T3, topcoat. The post-color coating composition of statement T1 wherein the topcoat composite comprises a plurality of polymeric particles, formed of a polymeric composite having neutralized acid moieties, wherein, in each of at least a portion of said polymeric particles, said polymeric composite envelops at least one polymeric particle; and, wherein said polymeric composite having said neutralized acid moieties includes neutralized alkene-(meth)acrylic acid copolymer and/or neutralized acrylamide/acrylate copolymer wherein the polymer is selected from:

a) neutralized ethylene-acrylic acid (EAA) copolymer.

b) neutralized ethylene-methacrylic acid (EMAA) copolymer.

c) neutralized acrylamide/acrylic acid (AAA) copolymer.

Statement T4, topcoat. The post-color coating composition of statement T1 wherein the topcoat composite is an aqueous dispersion comprising: a plurality of polymeric particles formed at least in part of a hydrophilic polymeric composite having neutralized acid moieties, wherein at least a part of the hydrophilic polymer composite in at least a portion of said polymeric particles envelops at least one pigment core particle, and wherein the polymeric particles are dispersed within the aqueous dispersion; and the composition being adapted to produce a pigmented polymeric layer. Statement T5, topcoat. The post-color coating composition of Statement T1 wherein the topcoat composite comprises a wear resistant olefinic polymer, a sacrificial non-sticky substance, a polyester, a poly (higher alkyl (meth)acrylate), a shellac, a volatile organic solvent, a fragrance and any combination thereof. Statement T6. A method for top coating a color coating on keratin fibers comprising applying a topcoat composite of any of statements T1-T5. Statement T7. A method according to statement T6 wherein the topcoat composite is contained in an aerosol container under pressure and is applied as a spray to the keratin fibers with color coating. Statement T8. A method according to statement T7 wherein the topcoat composite is diluted with a C4-C6 perfluoro hydrocarbon and/or carbon dioxide which act as a propellant.

Post Care Compositions

Statement 1, post care. A care composition for caring for a color coating of keratin fibers comprising a medium and a surface care active for overcoating the color coating. Statement 2, post care. The care composition of Statement 1 wherein the surface care active is a lubricating agent, a sacrificial agent, a feel modifier, an antifade agent or a combination thereof. Statement 3, post care. The care composition of statement 1, post care, wherein the surface care active is a polymeric or long chain non-polymeric nonionic surfactant or cationic surfactant having a non-penetrating property. Statement 4, post care. A method comprising applying a care composition of any of statements 1-3 to a color coating on keratin fibers. Statement 5. A topcoat-care composition comprising a combination of a care composition of any of statements 1-3 and a topcoat composite of any of statements T1-T5. Statement 6. A method comprising applying the topcoat-care composition to a color coating on keratin fibers.

Removal Methods

Statement R¹. A method for removing the color coating from keratin fibers comprising contacting the color coating with an organic hydrocarbon medium comprising at least dodecyl benzene sulfonic acid and isodecane. Statement R². A statement of a method according to statement R¹ wherein the removal composition is applied to the keratin fibers and thoroughly manipulated throughout the fibers for a period of at least 10 to 15 minutes. Statement R³. A statement of a method according to statement R² further comprising using an absorbable substrate to wipe the hair to take away the removal composition from the hair after manipulation. Statement R⁴. A statement of a method according statement R³ wherein the absorbable substrate is a cotton cloth or one or more paper towels. Statement R⁵. A statement of a method according to statement R⁴ further comprising shampooing and rinsing the hair following elimination of the removal composition from the hair.

Miscellaneous Statements

The invention has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any patient matter from the genus, regardless of whether or not the excised material is specifically recited herein. The inventions, examples, results and statement of embodiments described, stated and claimed herein may have attributes and embodiments include, but not limited to, those set forth or described or referenced in this application.

The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intent in the use of such terms and expressions to exclude any equivalent of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention as claimed and as provided by the statements of embodiments. Thus, it will be understood that although the present invention has been specifically disclosed by various nonlimiting embodiments and/or preferred nonlimiting embodiments and optional features, any and all modifications and variations of the concepts herein disclosed that may be resorted to by those skilled in the art are considered to be within the scope of this invention as defined by the appended claims and the statements of embodiments.

All patents, publications, scientific articles, web sites and other documents and ministerial references or mentioned herein are indicative of the levels of skill of those skilled in the art to which the invention pertains, and each such referenced document and material is hereby incorporated by reference to the same extent as if it had been incorporated verbatim and set forth in its entirety herein. The right is reserved to physically incorporate into this specification any and all materials and information from any such patent, publication, scientific article, web site, electronically available information, text book or other referenced material or document.

The written description of this patent application includes all claims, examples and statements of embodiments. All claims and statements of embodiments including all original claims are hereby incorporated by reference in their entirety into the written description portion of the specification and the right is reserved to physically incorporated into the written description or any other portion of the application any and all such claims and statements of embodiments. Thus, for example, under no circumstances may the patent be interpreted as allegedly not providing a written description for a claim on the assertion that the precise wording of the claim is not set forth in haec verba in written description portion of the patent.

While the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims and the statements of embodiments. Thus, from the foregoing, it will be appreciated that, although specific nonlimiting embodiments of the invention have been described herein for the purpose of illustration, various modifications may be made without deviating from the scope of the invention. Other aspects, advantages, and modifications are within the scope of the following claims and the present invention is not limited except as by the appended claims and the statements of embodiments.

The specific methods and compositions described herein are representative of preferred nonlimiting embodiments and are exemplary and not intended as limitations on the scope of the invention. Other objects, aspects, and embodiments will occur to those skilled in the art upon consideration of this specification and are encompassed within the spirit of the invention as defined by the scope of the claims. It will be readily apparent to one skilled in the art that varying substitutions and modifications may be made to the invention disclosed herein without departing from the scope and spirit of the invention. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, or limitation or limitations, which is not specifically disclosed herein as essential. Thus, for example, in each instance herein, in nonlimiting embodiments or examples of the present invention, the terms “comprising”, “including”, “containing”, etc. are to be read expansively and without limitation. The methods and processes illustratively described herein suitably may be practiced in differing orders of steps, and that they are not necessarily restricted to the orders of steps indicated herein or in the claims.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art. 

1. A method for producing a color coating on the surfaces of keratin fibers comprising Preparing the keratin fibers to form primed and/or deep cleaned keratin fibers; Applying to the primed and/or deep cleaned keratin fibers a pretreatment composition to form pre-coated keratin fibers; and Applying to the pre-coated keratin fibers a film forming composition to form a composite film of the film forming composition and pretreatment composition on the keratin fibers; and, Converting the composite film to a color coating on the keratin fibers; wherein The pretreatment composition comprises a compatible medium and at least one organosilicone small molecule with alkoxysilyl groups and/or organoamine groups; The film forming composition comprises a compatible medium with one or more microparticle pigments and/or color bodies, a binder, and a linker wherein the binder comprises an olefinic polymer, silicone polymer or olefinic-silicone block copolymer having at least 2 pendant and/or terminal carboxylic acid groups; and the linker comprises an alkylenyl, aromatic or alkylenyl aromatic polymer having multiple in chain segments of carbodiimide or a polymer of ester, urethane or urea monomeric residues having pendant and/or terminal alkylenyl single carbodiimide groups, wherein the binder and linker are each independently linear or branched, preferably linear; and, The primed and/or deep cleaned keratin fibers are prepared by removal of sebum and associated substances on the keratin fiber surfaces.
 2. A method according to claim 1 wherein the binder comprises at least at least three carboxylic acid groups.
 3. A method according to according to claim 1 wherein the binder comprises an olefinic-silicone block polymer.
 4. A method according to according to claim 1 wherein the linker further comprises pendant and/or terminal alkoxysilyl groups.
 5. A method according to claim 1 wherein the binder comprises a olefinic, silicone or organosilicone polymer of Formula I MUE-(MU1)_(x)(MUX)_(y)-(MU2)_(z)-(MU3)_(a)(MU3X)_(b)-MUE   Formula I wherein MU1 comprises a hydrophobic olefinic monomeric unit comprising a C2-C10 alkene residue, a C4-C12 alkadiene residue and/or a C6-C10 aromatic/alkylaromatic vinyl residue; MUX comprises an acidic olefinic monomeric unit comprising a C3-C10 alkenoic acid residue or a C4-C10 alkadienoic acid residue; MU2 comprises a hydrophilic olefinic monomeric unit comprising a vinyl C2-C16 alkanoic ester residue, a C1-C14 alkyl or hydroxyalkyl linear C2-C14 alkenoic ester residue, a C2-C10 alkenoic amide residue or N—C1-C4 alkyl substituted version of the amide residue; MU3 comprises a dimethylsiloxane residue; MU3X comprises a monomethylsiloxane residue bound to an alkanoic acid of at least 4 carbons with one of the alkyl carbons of the alkanoic acid optionally having a hydroxy group; and MUE comprises a single terminal monomeric unit of MU1, MU2, MU3, MUX or MU3X; each of the designators x, y, z, a and b independently designates the number of corresponding monomeric units forming the linear polymeric backbone, wherein each of x, z and a is zero or an integer of from 1 up to about 100,000 and y and b are each zero or an integer of 1 to 100; when b is an integer, y may be zero or an integer and when b is zero, y is an integer; the sum of x, y, z, a and b is an integer of from about 3 up to about 1 million, preferably up to about 300,000, more preferably up to about 250,000, most preferably up to about 200,000; and the multiple monomeric units of MU1, MU2 and MU3 are randomly distributed or form blocks in Formula I and the multiple carboxylic acid monomeric units MUX and MU3X are randomly distributed among MU1, MU2 and MU3 units.
 6. A method according to claim 1 wherein each of designators x, z and a are 10 to 100, each of designators y and b independently is 1 to 50, terminal MUE is MUX or MU3X and the polymer is an organosilicone block copolymer.
 7. A method according to claim 1 wherein the linker comprises an organic polymer of Formula II, a polymer with in-chain carbodiimide groups or Formula X, a polymer with pendant single carbodiimide groups Z-(L-N═C═N—)_(p)—Z   Formula II (Poly)_(q)-(K)_(s)-(Poly)_(r)   Formula X wherein; for Formula II, p is an integer of at least 2; and L is an organic linker group comprising saturated aliphatic divalent radical, an aromatic divalent radical or an alkylaromatic divalent radical or a polymer or oligomeric divalent radical with repeating olefinic, carbonate, ester, ether, amide, urethane or urea linkages; For Formula X, each Poly is an organic polymer segment of amide or urea monomeric residue based upon a C3 to C6 alkane diamine and a C4-C10 alkane dicarboxylic acid or C4-C10 alkane diisocyanate, or an ester monomeric residue based upon a C3-C6 alkane diol and a C4-C10 alkane dicarboxylic acid and the designators q and r each being an integer of at least 2; K is a pendant carbodiimide group of Formula XI with s being an integer of at least 2

wherein R²⁰ is a C3 to C6 alkylenyl residue, R²¹ is a C3-C6 alkylenyl residue; For Formulas II and XI Z is a non-reactive or reactive terminal group of the polycarbodiimide; and, the multiple K's are randomly distributed along the Poly backbone.
 8. A method according to claim 1 wherein the linker is Formula II, L is a residue of toluene, diphenylmethane, phenyl, dicyclohexyl methane, methyl-3,5,5,-trimethylcyclohexane, hexane, cyclohexane, norbornane.
 9. A method according to claim 1 wherein the pretreatment composition comprises at least one organosilicone small molecule comprising at least one pendant and/or terminal alkoxysilyl group and no or at least one pendant and/or terminal organoamine group.
 10. A method according to claim 1 wherein the small molecule of the pretreatment composition has Formula III [(H₂N)—((CH₂)_(m)—NH)_(o)—(R¹⁴)_(n))]_(a)—[RO_(t)Me_(3-t)Si—O]_(b)—(—SiMe₂-O)_(p)—(—SiMeOR—O)_(q)—[(—SiMe_(2-r′)[(CH₂)_(m′)—NH₂]_(r)—O]_(s)-[A]_(c)-[(—SiMeMe_(2-v)-O]_(u)—SiMe_(3-t)OR_(t)   Formula III wherein R may be methyl or ethyl; R¹⁴ is a C1-C6 alkylenyl group; Designators m and m′ may be an integer of 1 to 3; Designators o, n, b, r, s, c, u may be zero or 1; Designator a may be zero, 1 or 2; Designator v may be zero, 1 or 2 such that when a is 2, v is 2 and when a is 1, v is 1 and when a is zero, v is 1 or zero; Designator t may be 1 to 3; Designators p and q independently may be zero or an integer of 1 to 6; Designator t may be zero or an integer 1-3; Group A may be a divalent group including dithio, diazo, urethanyl, ureido, or C1-C6 alkylenyl connecting left and right sections of the small molecule, or Group A may be a terminal group including C1-C14 alkyl, C1X-C14X alkyl wherein X is N, S or O and X may be in-chain or terminal, C1-C6 alkoxy, C7-C14 arylalkyl, C6X-C14X heteroarylalkyl with X as N, S or O; C1-C6 alkylenyl(meth)acrylate or C1-C6 alkylureido.
 11. A method according to claim 1 wherein the small molecule of the pretreatment composition is aminopropyl triethoxysilane (APTES), trimethoxysilyl propyldiethylene triamine (SCA), trimethoxylsilyl propoxy (meth)acrylate ester (MEMO), propyl triethoxysilane (PTEO), ureidotrimethoxysilane (UREIDO), phenylsilane (PHS), tetraethoxysilane (TEOS), propylenyl or butenyl bis(trimethoxysilane) or C2-C6 mercaptoalkyl trimethoxy or triethoxysilane.
 12. A method according to claim 1 further comprising a pretreatment composition of an amine polymer, preferably polyethyleneimine instead of or in combination with a small molecule.
 13. A method according to claim 1 further comprising priming and/or deep cleaning the keratin fibers by applying a Prepaeratur and/or a Fundamenta technique to the fibers, wherein the Prepaeratur and/or Fundamenta techniques comprise a Prepaeratur step of treating the keratin fibers with a substantially non-conditioning or a non-conditioning surfactant composition to produce primed keratin fibers; and a Fundamenta step of deep cleaning the surfaces of the keratin fibers to form deep cleaned keratin fibers.
 14. A method according to claim 1 wherein the deep cleaning is accomplished by application of at least one of a cold plasma, phase transfer tenside, an oxidizing compound or a combination thereof to the surfaces of the keratin fibers whereby the deep cleaning at least partially removes F layer fatty acid, sebum and optionally adjusts the topography at the surfaces of the keratin fibers.
 15. A method according to claim 1 wherein the composite film on keratin fibers is converted to a color coating by drying and curing. 